|Publication number||US5385776 A|
|Application number||US 07/976,600|
|Publication date||Jan 31, 1995|
|Filing date||Nov 16, 1992|
|Priority date||Nov 16, 1992|
|Also published as||CA2148913A1, EP0668888A1, WO1994011430A1|
|Publication number||07976600, 976600, US 5385776 A, US 5385776A, US-A-5385776, US5385776 A, US5385776A|
|Inventors||MacRae Maxfield, Brian R. Christiani, Sanjeeva N. Murthy, Harold Tuller|
|Original Assignee||Alliedsignal Inc.|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (11), Non-Patent Citations (4), Referenced by (314), Classifications (22), Legal Events (5)|
|External Links: USPTO, USPTO Assignment, Espacenet|
1. Field of the Invention
This invention relates to a composite material comprising a polymer matrix having dispersed therein anisotropic nanometer size particles such as organophilic platelet particles derived from swellable intercalated layered materials and inorganic fibrillar materials, and to articles of manufacture formed from the composite material of this invention. More particularly, this invention relates to such composite materials and composites where polymer matrix is formed of a polymer in the gamma phase.
2. Prior Art
Polyamides may exist in various crystalline forms. Two principal crystalline forms of nylon 6, alpha and gamma, have been characterized structurally and thermodynamically (see, for example, Polymer Communications, 1991, 301 and references cited therein).
Various additives have been used to modify Nylon 6 which increases the rate of crystallization to the alpha or gamma form. See, for example, U.S. Pat. Nos. 4,397,979 and 4,290,935 and Japanese Patent 55-149346).
Polyamides, such as nylon 6, comprising a dispersion of particles, derived from organophilic phylosilicates and having a thickness of about 5 Å to about 12 Å, have been reported in the literature. See for example U.S. Pat. Nos. 4,739,007 and 4,810,734, and Kokai Publication No. 109998/76.
This invention relates to a composite comprising a polymer matrix comprising at least one gamma phase polyamide wherein at least about one weight percent of said polyamide based on the total moles of said polyamide is in the gamma phase, said polymer matrix having dispersed therein up to less than about 0.5% by wt. of the matrix of a namometer-scale particulate material selected from the group consisting of layered material having a thickness equal to or less than about 200 Å and fibrillar materials having a diameter equal to or less than about 100 Å. Another aspect of this invention relates to an article of manufacture comprising a body all or a portion of which is formed of the composite of this invention.
The composite of this invention exhibits several beneficial properties. For example, in the composite that portion of the polymer in the gamma phase crystalline form is resistant to conversion to the alpha crystalline form. Moreover, in those instances where the gamma phase polymer is a polyamide such as Poly(epsilon-caprolactam)(nylon 6), the composition exhibits improved rigidity and water resistance strength (ASTM D638 and ASTM D790), while substantially retaining other properties such as toughness (ASTM D256), surface gloss (ASTM D0523) and abrasion resistance (ASTM D1044).
The composite of this invention includes two essential components. One essential component is a polymer matrix comprising a gamma phase polyamide where at least about 1 weight percent of said polyamide is in the gamma crystalline phase. As used herein a "gamma phase polyamide" is a semi-crystalline polyamide capable of forming two or more crystalline phases, and comprising at least one of the less stable crystalline phases as determined by x-ray diffraction (XRD), infrared spectroscopy (IR), differential scanning calorimetry (DSC) and nuclear magnetic resonance (NMR), as described in N. S. Murthy and H. Minor, Polymer, 31,pp. 996-1002 (1990). For example, nylon 6 is a gamma phase polyamide capable of forming two crystalline forms. The nylon 6 chain has a directionality so that adjacent chain segments in a crystalline phase can either be parallel or anti-parallel. In the more stable alpha phase, hydrogen bonds form between anti-parallel chain segments, while in the less stable gamma phase, hydrogen bonds form between parallel segments. By contrast, nylon 6,6 is not a gamma phase polymer and is capable of forming a single cystalline phase since its chain has no directionality.
Polyamides for use in the process of this invention may vary widely, the only requirement is that they are capable of gamma phase crystallinity and are preferably melt processible. As used herein, a "polyamide" is a substance composed of ten or more recurring carbonamide monomeric units which may be the same or different. In the preferred embodiments of the invention, the polyamide includes at least thirty recurring monomeric units. The upper limit to the number of recurring monomeric units is not critical, provided that the melt index of the polymer under use conditions is such that the polymamide forms a composite material which can be processed into articles of this invention. More preferably, the polyamide includes at least from about 30 to about 100 recurring monomeric units. In the most preferred embodiments of this invention, the number of recurring units is such that the polyamide has a melt index of from about 0.01 to about 12 grams per 10 minutes, preferably from about 0.01 to about 10 grams/10 minutes and more preferably from about 0.5 to about 10 grams/10 minutes as measured by ASTM Test No. D-1238 at a load of 1000 grams at the processing temperature.
Illustrative of useful polyamides capable of gamma phase crystallinity are those formed from the polymerization of amino acids and derivatives thereof as for example lactams. Such polyamides include nylon 4, nylon 9, nylon 11, nylon 6, nylon 12, nylon 8, nylon 10, nylon 18 and the like. Preferred gamma phase polyamides are those formed by reaction of amino acids or derivatives thereof such as lactams. More preferred gamma phase polyamides are nylon 11, nylon 6 and nylon 12, and most preferred are nylon 6 and nylon 12. Nylon 6 is the gamma phase polymer of choice, especially where the nylon 6 has a melt index from about 0.01 to about 10 grams/10 minutes, and preferably from about 0.5 to about 10 grams/10 minutes as measured by ASTM Test No. D-1238 at a load of 1000 grams at 235° C.
The fraction of the polyamide having gamma phase crystallinity may vary widely. In general, the amount of the polyamide in the gamma phase is at least about 1 weight % based on the total weight of the polyamide. The amount of polyamide having gamma phase crystallinity is preferably at least about 10 weight % more, preferably from about 10 to about 50 weight % of the polyamide and most preferably from about 20 to about 50 weight % on the aforementioned basis. In the embodiments of choice, the amount of polyamide in the gamma phase is from about 30 to about 50 weight percent based on the total weight of the polyamide.
As a second essential ingredient, the composite of this invention includes dispersed particles selected from the group consisting of layered and fibrillar inorganic materials. Useful inorganic fibrillar materials may vary widely and are those having average diameters equal to or less than about 100 Å with a maximum diameter of 200 Å, preferably from about 10 to about 100 Å with a maximum diameter of 200 Å, more preferably from about 10 to about 50 Å with a maximum diameter of 100 Å, and most preferably from about 10 to about 20 Å with a maximum diameter of 50 Å. The average length of useful fibrillar materials may vary widely and is usually equal to or less than about 2,000 Å with a maximum length of about 10,000 Å, preferably from about 200 to about 2,000 Å with a maximum length of about 5,000 Å, more preferably from about 300 to about 2,000 Å with a maximum length of 2000 Å and most preferably from about 400 to about 1,000 Å with a maximum length of about 2,000 Å. Illustrative of useful fibrillar materials are imogolite and vanadium oxide.
Useful layered materials are those in which layers have an average thickness equal to or less than about 25 Å with a maximum thickness of 100 Å, preferably from about 5 Å to about 25 Å with a maximum thickness of 75 Å, more preferably from about 5 Å to about 20 Å with a maximum thickness of 50 Å, and more preferably from about 7 Å to about 25 Å with a maximum thickness of 25 Å.
Layered materials for use in this invention may vary widely and include phyllosilicates. Illustrative of such materials are smectite clay minerals such as montmorillonite, nontronite, beidellite, volkonskoite, hectorite, saponite, sauconite, magadiite, and kenyaite; vermiculite; and the like. Other useful layered materials include illite minerals such as ledikite and admixtures of illites with the clay minerals named above. Other useful layered materials, particularly useful with anionic polymers, are the layered double hydroxides, such as Mg6 Al3.4 (OH)18.8 (CO3)1.7 H2 O (see W. T. Reichle, J. Catal., 94 (12985) 547), which have positively charged layers and exchangeable anions in the interlayer spaces. Other layered materials having little or no charge on the layers may be useful in this invention provided they can be intercalated with swelling agents which expand their interlayer spacing. Such materials include chlorides such as FeCl3 and FeOCl, chalcogenides such as TiS2, MoS2, and MoS3, cyanides such as Ni(CN)2, and oxides such as H2 Si2 O5, V6 O13, HTiNbO5, Cr0.5 V0.5 S2, W0.2 V2.8 O7, Cr3 O8, MoO3 (OH)2, VOPO4 --2H2 O, CaPO4 CH3 --H2 O, MnHAsO4 --H2 O, Ag6 Mo10 O33, and the like. Preferred swellable layered materials are phyllosilicates of the 2:1 type having a negative charge on the layers ranging from about 0.25 to about 0.9 charges per formula unit and a commensurate number of exchangeable cations in the interlayer spaces. Most preferred layered materials are smectite clay minerals such as montmorillonite, nontronite, beidellite, bolkonskoite, hectorite, saponite, sauconite, magadiite, and kenyaite.
The amount of layered or fibrillar material included in the composite material, that is sufficient to result in a significant increase in the gamma content of a gamma phase polymer, is as little as about 5 ppm by weight.
The amount of layered and fibrillar material included in the composite material may vary widely depending on the intended use of the composite provided that the amount is less than about 0.5% by weight of the matrix. The lower amount is not critical provided that the amount is sufficient to provide the advantages of this invention. For example, the amount of such materials may be as low as about 5 ppm. Preferably the amount of layered or fibrillar material included is equal to or greater than about 10 ppm, more preferably equal to or greater than about 20 ppm and equal to or less than about 0.4% by weight, and most preferably equal to or greater than about 100 ppm and equal to or less than about 0.3% by weight.
The layered and fibrillar materials are substantially homogeneously dispersed in the gamma phase polymer matrix. In the case of layered materials, the layered material is dispersed as platelet particles. As used herein, "platelet particles" are particles having two relatively flat opposite faces wherein the thickness of which is the distance between the faces, which is relatively small compared to the size of the faces. The platelet particles dispersed in matrix polymers may have the thickness of the individual layers, or small multiples less than about 10, preferably less than about 5 and more preferably less than about 3 of the layers, and still more preferably 1 or 2 layers. The other dimensions of the platelet particles may vary greatly, but in the case of particles derived from clay minerals, the particle faces are roughly round or oblong having average diameters between about 10,000 Å and about 50 Å, such that the aspect ratio length/thickness ranges from about 1000 to about 1. For the purposes of the present invention, the average diameter is defined as the diameter of a circle having an area equal to the surface area of one broad surface face of the platelet shaped particle. The average diameter is determined from particle surface area as measured with a Leitz Texture Analyzer System in a fully computerized and automated mode. In the preferred embodiments of the invention, the average thickness of the platelet particles is equal to or less than about 20 Å with a maximum thickness of 50 Å and the average diameter is between 5,000 Å and 100 Å with a maximum diameter of 10,000 Å. More preferably, the average thickness is equal to or less about 15 Å with a maximum thickness of 25 Å and the average diameter is from about 2,000 Å to about 200 Å with a maximum diameter of 5,000 Å. Most preferably, the average thickness is from about 5 to about 15 Å with a maximum thickness of 25 Å and the average diameter is from about 2000 Å to about 200 Å with a maximum diameter of 5,000 Å.
The average interparticle spacing between layers of the layered materials and fibrils of the fibrillar materials may vary widely depending on the concentration of materials. In general, the higher the concentration of material in the polymer matrix the smaller the interparticle spacing; and conversely, the lower the concentration of material, the larger the interparticle spacing. In general, interparticle spacing is equal to or greater than about 15 Å to about 40 microns. The interparticle spacing is preferably equal to or greater than about 30 Å to about 20 microns, more preferably equal to greater than about 50 Å to about 5 microns, and most preferably equal to or greater than about 100 Å to about 1 micron.
As used herein "uniformly dispersed" is defined as a degree of dispersion of the particles having a standard deviation in particle density, down to a sampling volume of 10-15 m3 as determined by transmission electron microscopy. The degree of dispersion is preferably less than about 50% of the mean, more preferably less than about 30% of the mean, and most preferably less than about 20% of the mean.
The composite material of this invention may include various optional components which are additives commonly employed with polyamides. Such optional components include nucleating agents, fillers, plasticizers, impact modifiers, chain extenders, plasticizers, colorants, uv stabilizers, thermal stabilizers, mold release lubricants, antistatic agents, pigments, fire retardants, and the like. These optional components and appropriate amounts are well known to those of skill in the art, accordingly, only the preferred optional components will be described herein in detail.
The composite of this invention can be formed by any suitable process for forming the composite of this invention. For example, the composite of this invention can be conveniently prepared by in-reactor blending processes of the type described in U.S. Pat. Nos. 4,739,007 and 4,810,734 in which a monomer precursor of the polyamide such as a lactam is polymerized using some suitable techniques as for example, condensation polymerization, anionic polymerization, hydrolytic polymerization and the like, in the presence of a swollen and compatibilized particulate material. For example, in one such procedure montmorillonite intercalated with protonated 11-aminoundecanoic acid is combined with caprolactam and aminocaproic acid, in a ratio of 4:95:1 by weight. The mixture is stirred at 255° C. for three hours in an inert atmosphere, during which time the caprolactam and amino acid react substantially to yield a polyamide. Platelet particles comprising one or a few layers of montmorillonite are dispersed through the polyamide. The composite of this invention is preferably prepared via a melt blending process in which one or more gamma phase polyamides and one or more compatibilized particulate materials are sheared in the melt at a temperature equal to or greater than the melting point of at least one polyamide in the mixture until the particulate materials exfoliate and disperse to the desired extent. For example, a suitable polyamide such as pellets of nylon 6 and the desired amount of a particulate material such as montmorillionite is heated to a temperature sufficient to form a polyamide melt which is then sheared by some suitable means. In the preferred embodiments of the invention, mechanical shearing methods are employed such as by extruders, injection molding machines, Banbury® type mixers, Brabender® type mixers and the like. In the more preferred embodiments of the invention, shearing is achieved by introducing the polymer melt at one end of an extruder (single or double screw) and receiving the sheared polymer at the other end of the extruder. The temperature of the polymer melt, residence time of the melt in the extruder and the design of the extruder (single screw, twin screw, number of flights per unit length, channel depth, flight clearance, mixing zone etc.) are several variables which control the amount of shear to be applied.
The melt of the swellable intercalated material and the polyamide is subjected to shear mixing until the desired amount of material exfoliates to the desired extent. In general, at least about 80% by weight, preferably at least about 85% by weight, more preferably at least about 90% by weight and most preferably at least about 95% by weight of the material delaminate to form fibrils or platelet particles substantially homogeneously dispersed in the polymer matrix.
In either the in-reactor blending process or the melt blending process, useful layered and fibrillar inorganic materials are preferably those which have been swollen and intercalated between layers or fibrils with an organophilic intercalant which weaken the interlayer cohesive energy between layers and fibrils by swelling the interlayer or interfibril distances. In the preferred embodiments of the invention, the intercalant or intercalants increase the compatibility and bonding of the layers or fibrils with the polyamide melt by having attractive interactions with both the surfaces of the fibrils or layers and the polyamide. Intercalants which function to swell interlayer or interfibril distances are hereinafter referred to as "swelling agents", intercalants which function to increase the compatibility and bonding of the layers or fibrils with the polyamide melt are hereinafter referred to as "compatibilizing agents" and intercalants which function as swelling agents and compatibilizing agents are hereinafter referred to as "swelling/compatibilizing agents".
Swellable materials are materials comprising planar layers arrayed in a coherent, coplanar structure or fibrils, where the bonding within the layers or fibrils, is stronger than the bonding between the layers or fibrils such that the materials exhibit increased interlayer or interfibril spacing in their intercalation compounds. The neutral or ionic molecules, called "intercalants", may be introduced into the interlayer or interfibril spaces by either insertion, in the case of neutral molecules, or ion exchange, in the case of ions. The intercalants may be introduced in the form of a solid, liquid, gas, or solute. The intercalants may be introduced into the spaces between every layer or fibril, nearly every layer or fibril, or a large fraction of the layers or fibrils of the material such that the resulting particles comprise less than about 10 layers in thickness or fibrils in diameter. The particles are preferably less than about 8 layers in thickness or about 8 fibrils in diameter, more preferably less than about 5 layers in thickness or about 5 fibrils in diameter, and most preferably, about 1 or 2 layers in thickness or about for or two fibrils in diameter.
Swellable layered or fibril materials, such as the preferred smectite clay materials, generally require treatment by one or more intercalants to provide the required interlayer or interfibril swelling and/or polymer compatibility. The resulting interlayer or fibril spacing is critical to the performance of the intercalated layered material in the practice of this invention. As used herein the "inter-layer or interfibril spacing" refers to the distance between the faces of the layers or the distance between fibrils as they are assembled in the intercalated material before any delamination (or exfoliation) takes place. The preferred clay materials generally include interlayer or exchangeable cations such as Na+, Ca+2, K+, Mg+2 and the like. In this state, these materials do not delaminate in host polymer melts regardless of mixing, because their interlayer or interfibril spacings are usually equal to or less than about 4 Å consequently the interlayer or interfibril cohesive energy is relatively strong. Moreover, the metal cations do not aid compatibility between layers and fibrils and the polymer melt. In the preferred embodiments, these layered materials are intercalated by swelling agents of sufficient size to increase interlayer or interfibril distances to the desired extent. In general, the interlayer or interfibril distance should be at least about 4 Å, as determined by x-ray diffraction, in order to facilitate delamination of the layered material or fibril material at the nanoscale. In the preferred embodiments of the invention, the interlayer or interfibril distance is at least about 8 Å and more preferred interlayer or interfibril distances are at least about 15 Å. In these preferred embodiments, the swelling agent is a neutral organic molecule or an ionic species which is capable of exchanging with the interlayer or interfibril cations such as Li+, Na+, K+, Mg+2, and Ca+2 and is of sufficient size to provide the required interlayer or interfibril spacing. Such ionic species include NH4 +, Al+3, Cu2+, Fe+3, NH3 R1+, NH2 R1 R2+, NHR1 R2 R3+, NR1 R2 R3 R4+, where the R1, R2, R3 and R4 are the same or different and are organic substituents, and the like.
In order to further facilitate delamination of layered or fibril materials into platelet particles or fibrils, and prevent reaggregation of the particles, these layers and fibrils are preferably polymer-compatible. In cases where the polymer melt is not compatible with the layers, the swellable layered material or fibril material is intercalated by compatibilizing agents which consist of a portion which bonds to the surface of the layers and another portion which bonds or interacts favorably with the polymer. In some instances, intercalants are used which are swelling/compatibilizing agents which provide both the swelling function and the compatibilization function. Such agents preferably include a moiety or moieties which interact with the surface of the layers displacing, totally or in part, the original metal ions and which bonds to the surface of the layers; and includes a moiety or moieties whose cohesive energies are sufficiently similar to that of the polymer that the surface of the platelets is made more compatible with the polymer, thereby enhancing the homogeneity of the dispersion in the polymeric matrix. As used herein "compatible" refers to the extent to which the polymer matrix and the surface coating on the platelet particles (the compatibilizing agent) have a favorable interaction which promotes the intermingling of the matrix polymer and the surface layer in the interphase region. Compatibility derives from one or more of the following criteria: similar cohesive energy densities for the polymer and the derivatized platelets, similar or complimentary capacities for dispersive, polar, or hydrogen bonding interactions, or other specific interactions, such as acid/base or Lewis-acid/Lewis-base interactions. Compatibilization will lead to an improved dispersion of the platelet particles in the matrix and an improved percentage of delaminated platelets with a thickness of less than 50 Å.
The nature of the swelling/compatibilizing agent, swelling agent/compatibilizing agent will vary widely depending on the particular polymer and the particular layered material. For example, where the swellable layered material is a phyllosilicate as for example a smectite clay and the polyamide is a poly(lactam) such as poly(caprolactam), swelling/compatibilizing agents are preferably zwitterionic and ionic surfactant type molecules, and most preferably neutral organic molecules or zwitterionic and cationic surfactant type molecules. Useful neutral organic molecules include polar molecules such as amides, esters, lactams, nitrilies ureas, carbonates, phosphates, phosphonates, sulfates, sulfonates, nitro compounds, and the like. Preferred neutrals organics are monomus or oligomers of the natrix polymer. Useful cationic surfactants include onium species such as ammonium (primary, secondary, tertiary, and quaternary), phosphonium or sulfonium derivatives of aliphatic, aromatic or arylaliphatic amines, phosphines and sulfides.
Illustrative of such materials are oxonium compounds of the formula:
where X+ is an ammonium, sulfonium or phosphonium radical such as --NH3 +, --N(CH3)3 +, --N(CH3)2 (CH2 CH3)+, S(CH3)3, --+ P(CH3)3 --NH4 + (where R5 is --(CH)5 ═), and the like and R5 is an organic radical as for example substituted or unsubstituted alkyl, cycloalkenyl, cycloalkyl, aryl, or alkylaryl, either unsubstituted or substituted with amino, alkylamino, dialkylamino, nitro, azido, alkenyl, alkoxy, cycloalkyl, cycloalkenyl, alkanoyl, alkylthio, alkyl, aryloxy, arylalkylamino, alkylamino, arylamino, dialkylamino, diarylamino, aryl, alkylsulfinyl, aryloxy, alkylsulfinyl, alkylsulfonyl, arylthio, arylsulfinyl, alkoxycarbonyl, arylsulfonyl, alkylsilane, and a moiety of the formula:
(--ZCH2 --CHR')q --ZR6
wherein R6 is alkyl, cycloalkyl, aryl, R' is hydrogen, alkyl, or aryl, and Z is --O-- or --NR7 --, where R7 is hydrogen, alkyl, aryl or alkylsilane. Illustrative of useful R5 groups are hydrogen, alkyl, such as methyl, ethyl, octyl, nonyl, tert-butyl, neopentyl, isopropyl, sec-butyl, dodecyl and the like; alkenyl such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 1-heptenyl, 1-octenyl and the like; alkoxy such as propoxy, butoxy, methoxy, isopropoxy, pentoxy, nonoxy, ethyoxy, octoxy, and the like; cycloalkenyl such as cyclohexenyl, cyclopentenyl and the like; alkanoylalkyl such as butanoyl octadecyl, pentanoyl nonadecyl, octanoyl pentadecyl, ethanoyl undecyl, propanoyl hexadecyl and the like; amino; alkylaminoalkyl, such as methylamino octadecyl, ethylamino pentadecyl, butylamino nonadecyl and the like; dialkylaminoalkyl, such as dimethylamino octadecyl, methylethylamino nonadecyl and the like; arylaminoalkyl such as phenylamino octadecyl, p-methylphenylamino nonadecyl and the like; diarylaminoalkyl, such as diphenylamino pentadecyl, p-nitrophenyl-p'-methylphenylamino octadecyl and the like; alkylarylaminoalkyl, such as 2-phenyl-4-methylamino pentadecyl and the like; alkylsulfinyl, alkylsulfonyl, alkylthio, arylthio, arylsulfinyl, and arylsulfonyl such as butylthio octadecyl, neopentylthio pentadecyl, methylsulfinyl nonadecyl, benzylsulfinyl pentadecyl, phenylsulfinyl octadecyl, propylthiooctadecyl, octylthio pentadecyl, nonylsulfonyl nonadecyl, octylsulfonyl hexadecyl, methylthio nonadecyl, isopropylthio octadecyl, phenylsulfonyl pentadecyl, methylsulfonyl nonadecyl, nonylthio pentadecyl, phenylthio octadecyl, ethylthio nonadecyl, benzylthio undecyl, phenethylthio pentadecyl, sec-butylthio octadecyl, naphthylthio undecyl and the like; alkoxycarbonylalkyl such as methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl and the like; cycloalkyl such as cyclohexyl, cyclopentyl, cyclo-octyl, cycloheptyl and the like; alkoxyalkyl such as methoxy-methyl, ethoxymethyl, butoxymethyl, propoxyethyl, pentoxybutyl and the like; aryloxyalkyl and aryloxyaryl such as phenoxyphenyl, phenoxymethyl and the like; aryloryalkyl such as phenoxydecyl, phenoxyoctyl and the like; arylalkyl such as benzyl, phenethyl, 8-phenyloctyl, 10-phenyldecyl and the like; alkylaryl such as 3-decylphenyl, 4-octylphenyl, 4-nonylphenyl and the like; and polypropylene glycol and polyethylene glycol substituents such as ethyl, propyl, butyl, phenyl, benzyl, tolyl, p-styryl, p-phenylmethyl chloride, octyl, dodecyl, octadecyl, methoxy-ethyl, moieties of the formula --C3 H6 COOH, --C5 H10 COOH, --C7 H10 COOH, --C7 H14 COOH, --C9 H18 COOH, --C11 H22 COOH, --C13 H26 COOH, --C15 H30 COOH and --C17 H34 COOH and CH═C(CH3)COOCH2 CH2 --, and the like Such ammonium, sulfonium and phosphonium radicals are well known in the art and can be derived from the corresponding amines, phosphines, and sulfides.
Useful swelling/compatibilizing agents also include neutral compounds. For example useful swelling/compatibilizing agents include neutral amine, phosphine, and sulfide forms of the above-referenced oxonium compounds which hydrogen bond to the layers. In this case, the original metal cations are not replaced.
Another class of swelling/compatibilizing agents are those which are covalently bonded to the layers. Illustrative of such groups useful in the practice of this invention are silane coupling agents of the formula:
where R9 is the same or different at each occurrence and is alkyl, alkoxy or oxysilane such as trialkoxysilane compounds as for example octadecyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropylphenyldimethoxysilane, gamma-glycidoxypropyl tripropoxysilane, 3,3-epoxycyclohexylethyl trimethoxysilane, gamma-propionamido trithoxysilane, N-trimethoxysilylpropyl-N(beta-aminoethyl) amine, trimethoxysilylundecylamine, trimethoxy silyl-2-chloromethylphenylethane, trimethoxysilyl-ethylphenylsulfonylazide, N-trimethoxysilylpropyl-N,N,N-trimethylammonium chloride, N-(trimethoxysilylpropyl)-N-methyl-N,N-diallylammonium chloride, trimethoxysylilpropylcinnamate, 3-mercaptopropyl trimethoxysilane, 3-isocyanatopropyltriethoxysilane, and the like; and R8 is selected from the group consisting of organic radicals which are compatible with the polymer forming the composite.
In other instances, it is convenient to use a compatibilizing agent that is different from the swelling agent. For example, alkylammonium cations may be used to replace the metal cations of a smectite mineral, and be partially replaced, in turn, by a silane coupling agent. In this case, the alkylammonium cation functions as a general purpose swelling agent while the silane can function as a compatibilizing agent that is highly specific to a selected polymer system.
In the preferred embodiments of the invention, the swelling agent, compatibilizing agent and/or swelling/compatibilizing agent will include a moiety which bonds to the surface of the layered material and will not be reactive with the polymer. Preferably the agent will also include a moiety which does not bond with the layered material and which is compatible with the polymer. In the preferred embodiments of this invention, swelling/compatibilizing agents are employed, especially onium agents and silane agents. In the preferred embodiments of the invention lipophilic swelling and compatibilizing agents are used. Such agents will preferably include a lipophilic portion as for example a long chain alkyl, alkenyl or alkylaryl group (preferably of more than about 9 aliphatic carbon atoms). Such agents are well known in the art and include silane compounds and the ammonium, sulfonium and phosphonium derivatives of octadecylamine, octadecylphosphine, trimethyl dodecyl sulfide, octadecylsulfide, dimethyldidodecyl amine, octadecylamine, dioctylphosphine, methylocladecylamine, dioclysulfide, decylsulfide and the like.
The amount of swelling agent/compatibilizing agent and swelling/compatibilizing agents intercalated into swellable materials useful in this invention may vary substantially provided that the amount is effective to swell and, preferably to compatibilize the layers or fibrils of the intercalated material to the extent required to provide the desired substantially uniform dispersion. In the preferred embodiments of the invention where swelling/compatibilizing agents are employed, amounts of agents employed will preferably range from about 10 mmole/100 g of material to about 1000 mmole/100 g of material. More preferred amounts are from about 20 mmole/100 g to about 200 mmole/100 g. In the case of the preferred smectite clay minerals, the more preferred amounts are from about 80 mmole/100 g to about 120 mmole/100 g of layered material.
Swellable and polymer-compatible intercalated material can be formed by any method. Preferably such materials are formed by intercalation of suitable agent or agents in the interlayer or interfibril spaces of the swellable material by any suitable method. The swelling/compatibilizing agents are introduced into the interlayer or interfibril spaces of the swellable material by any suitable method as, for example, by either insertion of neutral molecules or by ion exchange with ionic molecules, using conventional procedures. Insertion of neutral molecules may be performed by exposing finely divided material to intercalants in the form of a gas, neat liquid, finely divided solid, or solute in a solvent which, preferably swells the material. Insertion is generally aided by exposure of the mixture of intercalant and layered material to shear, heat, ultrasonic cavitation, or microwaves. Ion exchange by ionic molecules may be performed by suspending the material in a relatively volatile liquid which is capable of both exfoliating and dispersing the layers or fibrils and dissolving a salt of the ionic intercalant as well as the resulting salt of the ion displaced from the material (e.g., Na+, Mg+2, Ca+2), adding the salt of the ionic intercalant, and removing the material (now complexed with the new intercalant) from the liquid (now containing the dissolved salt of the displaced ion). For example, swellable layered minerals such as montmorillonite and hectorite (having primarily Na+ cations in the interlayer spaces) intercalate water to the point that the layers are exfoliated and dispersed uniformly in water. Dispersion in water is generally aided by mixing with relatively high shear. A suitable swelling/compatibilization agent such as the hydrochloride salt of dimethyldodecylamine is then added in the desired amount after which the layers complexed with the ammonium cation are separated from the dispersion, washed of residual NaCl, and dried. In the preferred embodiments of the invention, the swellable layered material is intercalated by ion exchange. For example, a suspension of a montorillonite or a saponite in water, may be heated to about 80° C. and stirred using a high speed homogenizer mixer, in a concentration low enough to yield a low viscosity dispersion from which non-dispersible particles can be separated by sedimentation (mineral concentration of about 2% by weight, or 5% to 15% with addition of a peptizing agent such as sodium hexametaphosphate). The dispersion is combined with a solution of a suitable swelling/compatibilizing agent such as an ammonium salt (as, for example the hydrochlorides of octadecylamine, 11-aminoundecanoic acid dioctylamine, dimethyldodecylamine, methyloctadecylamine, dimethyldidodecylamine, and the like) such that the mole ratio of ammonium salt to exchangeable ions in the mineral is between 0.5 and 5. The amine-complexed layers may be separated from the solution by some suitable method such as filtration or centrifugation, followed by rinsing in fresh water, rough drying, and ball milling to about 100 mesh powder. The powder may be rigorously dried at 100° C. to 160° C. in vacuum for 8 to 24 h in the presence of a drying agent such as phosphorous pentoxide, to provide the desired swellable/polymer compatible intercalated layered material.
Intercalated layered materials intercalated with silanes may be formed by treating a swellable and polymer-compatible intercalated layered material already intercalated with an onium cation with a silane coupling agent in a swelling liquid, such as dioxane, glyme, diglyme, dimethylsulfoxide, methylethylketone, and the like, or by treating an aqueous suspension of a layered material with water-soluble silane coupling agents such as trialkoxysilanes. In the preferred embodiments, silane intercalated swellable/polymer compatible intercalated layered material is formed as follows: Onium-intercalated layered materials, preferably prepared as described above are suspended and swollen in a swelling organic liquid and treated with a trialkoxysilane. For example, montmorillonite intercalated with octadecylammonium cation, at about 80 mmole of ammonium cation/100 g mineral, is combined with dioxane to form a 5% by weight suspension which is heated to 60° C. and combined with a dioxane solution of aminoethylaminopropyl trimethoxysilane, such that the ratio of silane to mineral is about 20 mmole/100 g. The silane displaces the ammonium cation quantitatively to form a mixed intercalated layered material having about 60 mmole of ammonium cation and 20 mmole of silane per 100 g of mineral layers.
In the preferred embodiments of this invention, swellable and polymer-compatible intercalated layered compounds include montmorillonite (Gelwhite HNF, Southern Clay Products) complexed with octdecylammonium cation (100 mmole/100 g mineral), montmorillonite complexed (Volclay, American Colloids Company) with N,N-dimethyloctadecylammonium cation (100 mmole/100 g), synthetic hectorite (Laponite S, Laporte Industries) complexed with dimethyldioctylammonium cation (80 mmole/100 g), commercially available organoclay (Claytone APAR, Southern Clay Products), montmorillonite complexed with octadecylammonium cation (about 80 mmole/g) and derivatized with aminoethylaminopropyltrimethoxysilane (20 mmole/100 g), and the like.
For preferred use in forming nanocomposites, the swelling/compatibilizing agent is selected so that when subjected to the processing temperature of the matrix polymer(s), it does not evolve decompositions products which can cause chain scission or other degradation of the matrix polymers. Special care must be taken when polymers which require high processing temperatures are used. For example, quaternary ammonium cations start to thermally decompose at about 220° to 260° C. into alkenes and amines. On the basis of thermal stability, silanes and onium cations, that cannot undergo beta-elimination are preferred, e.g., ammonium cations of the formula:
[(R12)3 N--CR10 --CR11 ]+
where R10 is hydrogen or an organic moiety, R11 is an organic moiety and R12 is the same or different at each occurrence and is an organic radical.
The nanocomposite compositions according to the invention are thermoplastic materials from which molded articles of manufacture having valuable properties can be produced by conventional shaping processes, such as melt spinning, casting, vacuum molding, sheet molding, injection molding and extruding. Examples of such molded articles are components for technical equipment, apparatus castings, household equipment, sports equipment, bottles, containers, components for the electrical and electronics industries, car components, circuits, fibers, semi-finished products which can be shaped by machining and the like. The use of the materials for coating articles by means of powder coating processes is also possible, as is their use as hot-melt adhesives. The molding compositions according to the invention are outstandingly suitable for specific applications of all types since their spectrum of properties can be modified in the desired direction in manifold ways.
The compositions of this invention which include dispersed platelet particles are especially useful for fabrication of extruded films and film laminates, as for example, films for use in food packaging. Such films can be fabricated using conventional film extrusion techniques. The films are preferably from about 10 to about 100 microns, more preferably from about 20 to about 100 microns and most preferably from about 25 to about 75 microns in thickness. In the film, the major plane of the platelet fillers is substantially parallel to the major plane of the film. The extent of parallelism of particles and film can be determined by X-ray analysis. X-ray analysis is a useful way to described the crystallinity and orientation of polymer crystals and the orientation of platelet particles. A convenient method of X-ray analysis is that described in X-ray Diffraction Methods in Polymer Science, L. E. Alexander, Wiley, N.Y., pp. 137-229 (1969), hereby incorporated by reference.
For the purpose of the present invention Op, the platelet orientation factor, is an indication of the platelet particle orientation in the film. The Op was determined by making azimuthal scans from densitometer tracings of the X-ray photographs which were obtained by exposing the edge of the film to the incident X-rays. The angle is the angle between the reference direction, the normal to the film, and the normal to the plane of interest, the major plane of the platelet. The Op values were calculated as the average cosine square (<cos2 Φ>, where Φ is the angle between platelet normal and the film normal) for the normal to the flat faces of the platelet particles. An Op of 1.0 indicates that the faces of the platelets are completely parallel to the plane of the film. An Op of 0.0 indicates that the faces of the platelets are perpendicular to the plane of the film. The Op of the platelets in the film of the present invention is preferably from about 0.70 to about 1.0, more preferably from about 0.90 to about 1.0 and most preferably from about 0.95 to about 1.0. Such preferred orientation of platelet particles results in enhanced barrier properties and increased tare strength.
The homogeneously distributed platelet particles and polymer are formed into a film by suitable film-forming methods. Typically, the composition is melted and forced through a film forming die. The die can be a flat die or a circular die. A typical flat die is a hanger shaped die, and a typical circular die is a tubular film die.
The film of the nanocomposite of the present invention may go through steps to cause the platelets to be further oriented so the major planes through the platelets are substantially parallel to the major plane through the film. A method to do this is to biaxially stretch the film. For example, the film is stretched in the axial or machine direction by tension rollers pulling the film as it is extruded from the die. The film is simultaneously stretched in the transverse direction by clamping the edges of the film and drawing them apart. Alternatively, the film is stretched in the transverse direction by using a tubular film die and blowing the film up as it passes from the tubular film die. The films of this invention may exhibit one or more of the following benefits: increased modulus, wet strength, and dimensional stability, and decreased moisture absorption and permeability to gases such as oxygen and liquids such as water, alcohols and other solvents.
The following examples are presented to more particular illustrate the invention and should not be construed as limitation thereon.
Dilute nanocomposites of organoclay in nylon 6 were prepared by extruder compounding, and characterized by x-ray diffraction, XRD, of the extrudate and mechanical properties of their injection molded test samples.
The dilute nanocomposites were prepared from a dry mixture of (1) Bentone 34™ powder (a montmorillonite whose native interlayer cations were ion exchanged for dimethyldioctadecylammonium cation, obtained from Rheox, Inc.) and (2) unfilled nylon 6 pellets (Capron 8209F, obtained from Allied-Signal), by compounding the mixture using a twinscrew extruder equipped with general purpose mixing screws. Prior to compounding, the Bentone 34 powder was vacuum dried at 60° C. to a detectable moisture level of less than about 0.2%, and the nylon pellets were vacuum oven dried at 80° C. to a moisture level of less than about 0.1%. The mixture of Bentone 34 powder and nylon pellets was first compounded into a masterbatch which was determined by its ash content to be about 0.2% by weight inorganic, presumed to be aluminosilicate from the Bentone 34. Portions of this masterbatch were compounded with additional nylon 6 pellets to yield extrudate having calculated mineral concentrations of about 0.1, 0.05, and 0.01% by weight.
After vacuum drying, the final extrudates were analyzed by XRD and found to be, in general, about 65% amorphous, 30% in a gamma crystalline phase, and 5% in an alpha crystalline phase. The various nanocomposites plus an unfilled nylon 6 control were injection molded into test samples using an Arburgh injection molder, and a portion of set of samples was immersed in water for 21 days at a temperature of about 20° C. The flexural and tensile properties of these samples, both dry and wet, were determined according to the procedures of ASTM D790 and ASTM D638, respectively. The notched impact strengths of the dry samples were determined according to the procedures of ASTM D256, and their average values are set forth in Table 3. The flexural and tensile properties are set forth in Tables 1 through 4.
TABLE 1__________________________________________________________________________DRY AS MOLDED FLEXURAL PROPERTIES (ASTM D790)(injection molded samples) % change in % change flexural in flexural crystallinity modulus flexural strength strengthnylon: % alpha/ flexural modulus, relative to to 5% strain, psi relative toorganoclaya % gamma psi (MPa) unfilled nylon (MPa) unfilled nylon__________________________________________________________________________N6: 20/8 401,000 (2,770) 0 15,700 (108) 0unfilled:0.01% <5/30 444,000 (3,070) 11% 17,300 (120) 10%:0.05% <5/30 453,000 (3,130) 13% 18,000 (124) 15%:0.10% <5/30 458,000 (3,160) 14% 18,000 (124) 15%N66: 20 445,000 (3,070) 0 17,100 (118) 0unfilled:0.01% 20 448,000 (3,100) 1% 17,400 (120) 2%:0.05% 20 451,000 (3,120) 1% 17,400 (120) 2%:0.10% 20 457,000 (3,160) 3% 17,400 (120) 2%__________________________________________________________________________ a weight percent clay mineral derived from Bentone 34 (montmorillonite complexed with quaternary ammonium cation)
TABLE 2__________________________________________________________________________WATER-SATURATED FLEXURAL PROPERTIES (ASTM)D790)(injection molded samples immersed 3 weeks in water) % change in % change flexural in flexural crystallinity modulus flexural strength strengthnylon: % alpha/ flexural modulus, relative to to 5% strain, psi relative toorganoclaya % gamma psi (MPa) unfilled nylon (MPa) unfilled nylon__________________________________________________________________________N6: 36/8 60,400 (417) 2,550 (18)unfilled:0.01% 15/30 73,400 (507) 22% 3,160 (22) 24%:0.05% 15/30 79,900 (550) 32% 3,400 (24) 33%:0.10% 17/36 79,000 (546) 31% 3,400 (24) 33%N66: 100,200 (690) 4,000 (28)unfilled:0.01% 98,200 (678) 0% 3,900 (27) 0%:0.05% 101,800 (703) 2% 4,030 (28) 1%:0.10% 102,000 (705) 2% 4,030 (28) 1%__________________________________________________________________________ a weight percent clay mineral derived from Bentone 34 (montmorillonite complexed with quaternary ammonium cation).
TABLE 3__________________________________________________________________________DRY AS MOLDED TENSILE PROPERTIES (ASTM D638)(injection molded samples) % change in notched tensile yield tensile yield impact,nylon: stress, psi stress relative to ft. lb./inch elongation toorganoclay (MPa) unfilled nylon (J/m) break, %__________________________________________________________________________N6: unfilled 11,200 (77) -- 1.3 (69) 260%:0.01% 12,000 (83) 7% 1.2 (66) 150:0.05% 12,400 (86) 11% 1.2 (64) 90:0.10% 12,300 (85) 10% 1.2 (65) 100N66: unfilled 12,200 (84) -- 1.1 (58) 20:0.01% 12,200 (84) 0% 1.0 (54) 20:0.05% 12,200 (84) 0% 0.8 (44) 20:0.10% 12,300 (85) 1% 0.8 (45) 20__________________________________________________________________________
TABLE 4______________________________________WATER SATURATED TENSILE PROPERTIES(ASTM D638)(injection molded samples immersed in water 3 weeks) tensile % change in tensile elongationnylon: yield stress, yield stress relative to to break,organoclay psi (MPa) unfilled nylon %______________________________________N6: unfilled 3,100 (21) -- 300%:0.01% 3,900 (27) 26% 280:0.05% 4,200 (29) 35% 270:0.10% 4,100 (28) 32% 270N66: unfilled 5,600 (39) -- 300:0.01% 5,600 (39) 0% 250:0.05% 5,700 (39) 2% 250:0.10% 5,700 (39) 2% 260______________________________________
The strength and stiffness of dry nylon 6 are increased by at least 10% by the addition of dispersed organoclay at concentrations as low as 0.01% by weight(or about 0.005% by volume). At the same time, the toughness of dry nylon 6 (as suggested by the ultimate elongation and notched impact strength) is only slightly reduced by the addition of low concentrations of dispersed organoclay. At high moisture content, the strength and stiffness of nylon 6 are increased by at least 22% by the addition of dispersed organoclay.
Dilute nanocomposites of organoclay (Bentone 34, obtained from Rheox, Inc.) in nylon 66 (Zytel 101, obtained from DuPont) were prepared, injection molded, and characterized according to the procedures described in Example 1, and the results are set forth in Tables 1 through 4. According to their XRD patterns, these nylon 66 nanocomposites exhibited crystallinity that was substantially the same as unfilled nylon 66 which was about 20% in its alpha crystalline phase and which does not form a gamma crystalline phase.
Unlike those of nylon 6, the strength and stiffness of nylon 66 (both dry and water-soaked) were increased by only about 1% to 3% by the addition of dispersed organoclay at concentrations of 0.05% by weight or less. The toughness of dry nylon 66 (as indicated by ultimate elongation and notched impact strength) remained low compared to nylon 6.
A mixture of organoclay (Claytone APA™, a montmorillonite complexed with a tetraalkylammonium cation, obtained from Southern Clay Products, Inc.) and nylon 6 (Capron 8209F, obtained from Allied-Signal, Inc.) was extruded and injection molded into test samples whose Drop Weight Impact Strength was determined according to the procedures of ASTM D3029. The mineral content of the extrudate, estimated by its ash content, was about 0.018% by weight. The organoclay and nylon 6 were prepared and extruded according to the procedures described in Example 1. The results of the Drop Weight Impact test, along with those of flexural and tensile tests, are set forth in Table 5.
According to its XRD pattern, the nylon/organoclay composite extrudate was 40% crystalline and rich in gamma-phase crystallites.
TABLE 5__________________________________________________________________________GAMMA-RICH vs ALPHA-RICH NYLON 6:Flexural, Tensile, and Drop Weight Impact Properties(dry as molded) drop weight crystallinitya flexural stress to ultimate impact % alpha/% flexural modulus, 5% strain, Kpsi elongation, strength,filler gamma Kpsi (MPa) (MPa) % ft. lb.b__________________________________________________________________________0.018% 12/28 440 (3,040) 18 (124) 83 116clayfromClaytone0.20% 22/3 440 (3,040) 17 (117) 29 64talc,Microfine__________________________________________________________________________ a Crystallinity of extrudate determined by xray diffraction. b ASTM D3029, type A tup.
A mixture of microfine talc (ABT-2500, obtained from Pfizer) and nylon 6 (Capron 8209F) was extruded and injection molded into test samples whose Drop Weight Impact strength was determined according to the procedures of ASTM D3029. The mineral content of the extrudate, estimated by its ash content, was about 0.18% by weight.
A series of very dilute nylon 6/organoclay nanocomposites was prepared by first compounding Claytone APA with nylon 6 (Capron 8209F) following the procedures described in Example 1 to produce a masterbatch, and then re-extruding portions of the masterbatch with unfilled 8209F nylon 6. The mineral content of the resulting nanocomposites, as calculated based on the ash content of the masterbatch (0.018% by weight), were 0.009%, 0.0036%, and 0.0018% by weight. Injection molded samples of the dilute composites, unfilled 8209F nylon 6, and the talc-nucleated nylon 6 of Comparative Example 2 were characterized by XRD and tested for their mechanical properties according to the procedures of ASTM D790 and for their water uptake during prolonged immersion. The results of these tests are set forth in Table 6.
TABLE 6__________________________________________________________________________DILUTE N6/ORGANOCLAY COMPOSITES (ASTM D790)clay contenta, crystallinityb flexural stress toppm by % alpha/% gamma flexural modulus, 5% strain, Kpsi water uptake, % byweight (size & perfection) Kpsi (MPa) (MPa) weightc__________________________________________________________________________ 0 29/11 (64 A) 401 (2,770) 15.7 (108) 8.1 18 0/35 (95 A) 438 (3,030) 17.9 (124) 5.5 36 0/38 (110 A) 439 (3,030) 17.8 (123) 5.4 90 0/35 (100 A) 439 (3,030) 17.8 (123) 5.0 180 0/42 (120 A) 439 (3,030) 17.7 (123) 4.82,000 talc -- 440 (3,040) 17.0 (117) 6.5__________________________________________________________________________ a Mineral content derived from Claytone APA ™. b Crystallinity of 1/4 inch molded samples, based on XRD analysis. c Measured after two weeks of immersion in water at 20° C.
All of the dilute nylon 6/organoclay composites exhibited greater stiffness and strength than unfilled nylon 6 and greater resistance to water absorption than the talc-containing nylon 6 of Comparative Example 2. The molded samples characterized by XRD were found to consist of about 35 to 42% gamma crystalline nylon 6 and less than about 2% of the alpha form. In contrast, a sample of unfilled 8209F nylon 6, molded under the same conditions, was found to have comparable total crystallinity (40%), but with an alpha to gamma ratio of 72 to 28. The size and perfection of the crystallites increased with increasing clay content. The XRD patterns of the 0.0018% composite and the unfilled nylon 6 are shown in FIGS. 1 and 2.
A nylon 6/organoclay composite having about 0.27% clay mineral was prepared by compounding a mixture of powdered montmorillonite, complexed with protonated 11-aminoundecanoicacid, with nylon 6 pellets (Capron 8207F) according to the procedures described in Example 1.
The organoclay powder was prepared by combining a 4% dispersion of montmorillonite (Gelwhite HNF, obtained from Southern Clay Products) with an aqueous solution of 11-aminoundecanoicacid-HCl (100 mmole/100 g clay) at about 80° C. under high-shear mixing. The flocculated product was filtered, washed 4 times with hot water, dried at 60° C. in vacuum, tumbled in a ball mill, and passed through a 200 mesh screen. Pellets of nylon 6/organoclay composite and also pellets of a commercial gamma-rich nylon 6 (1017K, obtained from Toray) were annealed for 2 hours at various temperatures, and were characterized by their XRD patterns. The crystallinities of the samples after annealing are set forth in Table 7.
TABLE 7______________________________________GAMMA CRYSTALLINITY OF A NYLON 6/ORGANOCLAY NANOCOMPOSITE AFTERANNEALING FOR TWO HOURS (determinedby X-Ray Diffraction) PERCENT OF TOTAL CRYSTALLINITY IN GAMMA PHASEasample before anneal 195 C 200 C 205 C______________________________________0.27% claya 88% 42% 40% 33%Toray 1017K 65% 34% 32% 13%______________________________________ a Total crystallinity of each sample was about 50 to 60%.
Several different organoclays have been used to prepare nylon 6/organoclay nanocomposites following the procedures described in Example 1. These include organoclays derived from montmorillonite, hectorite, and a synthetic lithium-magnesium silicate (Laponite, obtained from LaPorte) treated with alkylammonium cations, organosilanes, and mixtures of onium cations and silanes.
Silane-treated minerals were prepared by combining a water or water/isopropanol solution the silane with a rapidly stirred 4% dispersion of the mineral in a like liquid (water or water/isopropanol). Generally, minerals treated with both silanes and ammoniun cations were prepared by first treating the mineral dispersion with the silane solution (in amounts insufficient to flocculate the mineral), and then the onium hydrochloride. The resulting organoclay was filtered, washed, and dried as described in Example 5. In some cases, minerals treated with both silanes and onium cations were prepared by adding silane to a rapidly stirred dispersion of previously prepared mineral fully complexed with an ammonium cation in refluxing isopropanol.
The crystallinities of these nanocomposites are set forth in Table 8.
TABLE 8__________________________________________________________________________CRYSTALLINITY OF NYLON 6a NANOCOMPOSITES OFVARIOUS ORGANOCLAYS mineral % % Xgamma Xgammamineral treatmentb content alphac gamma (XRD) (IR)d__________________________________________________________________________ control 0 20 8 0.29 0.3montmorillonite protonated 11- 2.0% <10 31 0.76 0.6 aminoundecanoic acidmontmorillonite protonated octadecylamine 2.0% <10 32 0.76 0.6montmorillonite protonated 1.0% <10 28 0.74 dipentylaminemontmorillonite octadecylsilane 2.0 <10 29 0.74 0.6montmorillonite chloromethylphenylethylsilane 2.0 <10 29 0.74montmorillonite octadecylsilane, 2.0 <10 28 0.74 0.5 chloromethylphenylethylsilane (10:1)montmorillonite protonated dipentylamine, 2.0 <10 36 0.78 glycidoxypropylsilane (10:1)hectorite protonated dipentylamine 0.02 <10 26 0.72hectorite protonated dipentylamine, 0.2 <10 30 0.75 protonated 11- aminoundecanoid acid (10:1)Laponite ™ protonated octadecylamine 1.0 10 35 0.78Laponite ™ protonated 11- 1.0 8 20 0.71 aminoundecanoic acid__________________________________________________________________________ b According to the weight loss observed when the organoclay were heated to 800° C., the amount of treatment generally corresponded to about 100 mmole/100 g of mineral. c The alpha phase in the nanocomposites was highly disordered an estimated to be not greater than 10%. d The absorbances of IR bands characteristic of alpha (928 cm-1 and gamma (977 cm-1) were compared with those of samples of known ratios of alpha and gamma nylon 6, following the procedure of Muraki (U.S Pat. No. 4,290,935)
Nylon 6 nanocomposites of organoclays were prepared by polymerizing caprolactam in the presence of suspended organophilic layered materials. The resulting nanocomposites, containing about 2% mineral, were found by XRD to comprise 35 to 45% gamma crystalline nylon 6 and less than 10% poorly crystallized alpha phase.
Montmorillonite, derived according to the procedure described in Example 1 and left wet, was rapidly stirred using a high shear mixer (Ross Mixer) with molten caprolactam and aminocaproic acid such that the mixture consisted of about 2.5% derivatized montmorillonite: 10% water: 85% caprolactam: and 2% aminocaproic acid. This mixture was heated to 255° C. under a flow of nitrogen with constant stirring for 5 h. After cooling, the crude product was milled into 1 mm-sized particles, stirred for 2 h in boiling water 3 times, and dried to a moisture content of less than about 0.1% by weight. Evaluation by XRD, both before and after injection molding, indicated gamma-rich crystallinity.
An immiscible blend of nylon 6, containing dispersed organoclay, and a rubber modifier exhibits increased flexural strength and modulus, relative to a similar blend containing no organoclay, while retaining its impact strength. The blend is prepared by (1) compounding nylon 6 with montmorillonite complexed protonated dipentyla ammonium cation in a twinscrew extruder such that the composite comprises about 0.2% mineral by weight, and (2) compounding the nylon 6/organoclay composite with a Zn ionomer of poly(ethylene-co-methacrylic acid) (Surlyn 9910, obtained from DuPont) such that the blend comprises about 20% by weight Surlyn. The resulting blend exhibits predominantly gamma crystallinity in its nylon 6 fraction, while the blend of Surlyn and nylon 6 exhibits predominantly alpha crystallinity in its nylon fraction.
A dilute composite of nylon 6 and particles of dispersed clay platelets, comprising no onium or organic groups covalently bonded to the clay, exhibits increased strength and rigidity, and predominantly gamma crystallinity. The composite is prepared by (1) mixing, at high shear, montmorillonite intercalated with Na+ cations with molten caprolactam and water in a ratio of about 1:3:1, (2) removing water from a powdered form of the mixture by vacuum drying, (3) compounding the mixture with nylon 6, in an extruder, and (4) leaching the caprolactam from the extrudate with boiling water.
A composite of nylon 6, organoclay, and glass fiber and all other non-nucleating fillers (nominally 1/8 inch in length), in a ratio of about 84.8:0.2:15 by weight, exhibits higher strength and stiffness relative to a similar composite containing no organoclay. The composite also exhibits predominantly gamma crystallinity in its nylon fraction. The composite is prepared by compounding nylon 6 hectorite complexed with protonated octadecylammonium cation, and then compounding this nanocomposite with glass fiber.
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US4290935 *||Oct 25, 1979||Sep 22, 1981||Toray Industries, Incorporated||Highly rigid polyamide composition|
|US4379979 *||Feb 6, 1981||Apr 12, 1983||The United States Of America As Represented By The Secretary Of The Navy||Controlled porosity sheet for thermionic dispenser cathode and method of manufacture|
|US4739007 *||Sep 19, 1986||Apr 19, 1988||Kabushiki Kaisha Toyota Chou Kenkyusho||Composite material and process for manufacturing same|
|US4810734 *||Mar 15, 1988||Mar 7, 1989||Kabushiki Kaisha Toyota Chuo Kenkyusho||Process for producing composite material|
|US4894411 *||Mar 14, 1988||Jan 16, 1990||Kabushiki Kaisha Toyota Chuo Kenkyusho||Composite material and process for producing the same|
|US5102948 *||May 2, 1990||Apr 7, 1992||Ube Industries, Ltd.||Polyamide composite material and method for preparing the same|
|DE3632865A1 *||Sep 26, 1986||Apr 2, 1987||Toyoda Chuo Kenkyusho Kk||Verbundmaterial und verfahren zu dessen herstellung|
|EP0398551A2 *||May 2, 1990||Nov 22, 1990||Ube Industries, Ltd.||Method for preparing a polyamide composite material|
|JPH0229458A *||Title not available|
|JPS50109998A *||Title not available|
|JPS55149346A *||Title not available|
|1||*||A New Dictionary of Chemistry Miall & Sharp 4th Edition p. 614.|
|2||A New Dictionary of Chemistry-Miall & Sharp-4th Edition-p. 614.|
|3||Murthy, N. S., "Metastable Crystalline Phases in Nylon 6", Polymer Communications, vol. 32, No. 1, (1991), pp. 301-305.|
|4||*||Murthy, N. S., Metastable Crystalline Phases in Nylon 6 , Polymer Communications, vol. 32, No. 1, (1991), pp. 301 305.|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US5530052 *||Apr 3, 1995||Jun 25, 1996||General Electric Company||Layered minerals and compositions comprising the same|
|US5552469 *||Jun 7, 1995||Sep 3, 1996||Amcol International Corporation||Intercalates and exfoliates formed with oligomers and polymers and composite materials containing same|
|US5578672 *||Jun 7, 1995||Nov 26, 1996||Amcol International Corporation||Intercalates; exfoliates; process for manufacturing intercalates and exfoliates and composite materials containing same|
|US5698624 *||Jun 7, 1995||Dec 16, 1997||Amcol International Corporation||Exfoliated layered materials and nanocomposites comprising matrix polymers and said exfoliated layered materials formed with water-insoluble oligomers and polymers|
|US5717000 *||Feb 20, 1997||Feb 10, 1998||The Dow Chemical Company||Despersions of delaminated particles in polymer foams|
|US5721306 *||Sep 8, 1995||Feb 24, 1998||Amcol International Corporation||Viscous carrier compositions, including gels, formed with an organic liquid carrier and a layered material:polymer complex|
|US5730996 *||May 23, 1996||Mar 24, 1998||Amcol International Corporation||Intercalates and expoliates formed with organic pesticide compounds and compositions containing the same|
|US5747575 *||Nov 1, 1996||May 5, 1998||Mitsubishi Chemical Corporation||Crystalline thermoplastic resin composition|
|US5760121 *||May 2, 1996||Jun 2, 1998||Amcol International Corporation||Intercalates and exfoliates formed with oligomers and polymers and composite materials containing same|
|US5804613 *||Dec 22, 1995||Sep 8, 1998||Amcol International Corporation||Intercalates and exfoliates formed with monomeric carbonyl-functional organic compounds, including carboxylic and polycarboxylic acids; aldehydes; and ketones; composite materials containing same and methods of modifying rheology therewith|
|US5830528 *||May 29, 1996||Nov 3, 1998||Amcol International Corporation||Intercalates and exfoliates formed with hydroxyl-functional; polyhydroxyl-functional; and aromatic compounds; composites materials containing same and methods of modifying rheology therewith|
|US5837763 *||Jan 3, 1996||Nov 17, 1998||Amcol International Corporation||Compositions and methods for manufacturing waxes filled with intercalates and exfoliates formed with oligomers and polymers|
|US5844032 *||Dec 6, 1996||Dec 1, 1998||Amcol International Corporation||Intercalates and exfoliates formed with non-EVOH monomers, oligomers and polymers; and EVOH composite materials containing same|
|US5849830 *||Oct 15, 1997||Dec 15, 1998||Amcol International Corporation||Intercalates and exfoliates formed with N-alkenyl amides and/or acrylate-functional pyrrolidone and allylic monomers, oligomers and copolymers and composite materials containing same|
|US5877248 *||Nov 12, 1997||Mar 2, 1999||Amcol International Corporation||Intercalates and exfoliates formed with oligomers and polymers and composite materials containing same|
|US5880197 *||Dec 22, 1995||Mar 9, 1999||Amcol International Corporation||Intercalates and exfoliates formed with monomeric amines and amides: composite materials containing same and methods of modifying rheology therewith|
|US5952093 *||Feb 20, 1997||Sep 14, 1999||The Dow Chemical Company||Polymer composite comprising a inorganic layered material and a polymer matrix and a method for its preparation|
|US5952095 *||Dec 6, 1996||Sep 14, 1999||Amcol International Corporation||Intercalates and exfoliates formed with long chain (C10 +) monomeric organic intercalant compounds; and composite materials containing same|
|US5955094 *||Nov 4, 1997||Sep 21, 1999||Amcol International Corporation||Intercalates and exfoliates formed with organic pesticides compounds and compositions containing the same|
|US5955535 *||Nov 29, 1993||Sep 21, 1999||Cornell Research Foundation, Inc.||Method for preparing silicate-polymer composite|
|US5962553 *||Sep 3, 1996||Oct 5, 1999||Raychem Corporation||Organoclay-polymer composites|
|US5969029 *||Oct 16, 1997||Oct 19, 1999||Sumitomo Chemical Company, Limited||Process for producing a gas barrier resin composition|
|US5998528 *||Feb 2, 1998||Dec 7, 1999||Amcol International Corporation||Viscous carrier compositions, including gels, formed with an organic liquid carrier, a layered material: polymer complex, and a di-, and/or tri-valent cation|
|US6050509 *||Mar 18, 1998||Apr 18, 2000||Amcol International Corporation||Method of manufacturing polymer-grade clay for use in nanocomposites|
|US6051643 *||May 26, 1998||Apr 18, 2000||Kabushiki Kaisha Toyota Chuo Kenkyusho||Resin composite and method for producing the same|
|US6057035 *||Jun 5, 1998||May 2, 2000||Triton Systems, Inc.||High-temperature polymer/inorganic nanocomposites|
|US6057396 *||Aug 11, 1997||May 2, 2000||Amcol International Corporation||Intercalates formed by co-intercalation of monomer, oligomer or polymer intercalants and surface modifier intercalants and layered materials and nonocomposites prepared with the intercalates|
|US6083559 *||Sep 22, 1998||Jul 4, 2000||Amcol International Corporation||Intercalates and exfoliates formed with hydroxyl-functional; polyhydroxyl-functional; and aromatic compounds; composite materials containing same and methods of modifying rheology therewith|
|US6084019 *||Dec 22, 1997||Jul 4, 2000||Eastman Chemical Corporation||High I.V. polyester compositions containing platelet particles|
|US6090734 *||Mar 18, 1998||Jul 18, 2000||Amcol International Corporation||Process for purifying clay by the hydrothermal conversion of silica impurities to a dioctahedral or trioctahedral smectite clay|
|US6126734 *||Sep 22, 1998||Oct 3, 2000||Amcol International Corporation||Intercalates and exfoliates formed with hydroxyl-functional; polyhydroxyl-functional; and aromatic compounds; composite materials containing same and methods of modifying rheology therewith|
|US6136908 *||Jun 17, 1999||Oct 24, 2000||Industrial Technology Research Institute||Preparation of thermoplastic nanocomposite|
|US6156835 *||Dec 22, 1997||Dec 5, 2000||The Dow Chemical Company||Polymer-organoclay-composites and their preparation|
|US6225374||May 19, 1999||May 1, 2001||Cornell Research Foundation, Inc.||Method for preparing silicate-polymer composite|
|US6225394||Jun 1, 1999||May 1, 2001||Amcol International Corporation||Intercalates formed by co-intercalation of onium ion spacing/coupling agents and monomer, oligomer or polymer ethylene vinyl alcohol (EVOH) intercalants and nanocomposites prepared with the intercalates|
|US6228903||Apr 1, 1999||May 8, 2001||Amcol International Corporation||Exfoliated layered materials and nanocomposites comprising said exfoliated layered materials having water-insoluble oligomers or polymers adhered thereto|
|US6235533||Mar 18, 1998||May 22, 2001||Amcol International Corporation||Method of determining the composition of clay deposit|
|US6238793||Oct 29, 1997||May 29, 2001||E. I. Du Pont De Nemours And Company||Method for production of a low density polyethylene-lamellar silicate composite material|
|US6242500||May 26, 2000||Jun 5, 2001||Amcol International Corporation||Intercalates and exfoliates formed with long chain (C6+) or aromatic matrix polymer-compatible monomeric, oligomeric or polymeric intercalant compounds, and composite materials containing same|
|US6251980||Mar 19, 1999||Jun 26, 2001||Amcol International Corporation||Nanocomposites formed by onium ion-intercalated clay and rigid anhydride-cured epoxy resins|
|US6262162 *||Mar 19, 1999||Jul 17, 2001||Amcol International Corporation||Layered compositions with multi-charged onium ions as exchange cations, and their application to prepare monomer, oligomer, and polymer intercalates and nanocomposites prepared with the layered compositions of the intercalates|
|US6265038||Jan 27, 1999||Jul 24, 2001||Tetra Laval Holdings & Finance, Sa||Transparent high barrier multilayer structure|
|US6271298 *||Apr 27, 2000||Aug 7, 2001||Southern Clay Products, Inc.||Process for treating smectite clays to facilitate exfoliation|
|US6287634||Dec 22, 1995||Sep 11, 2001||Amcol International Corporation||Intercalates and exfoliates formed with monomeric ethers and esters; composite materials containing same methods of modifying rheology therewith|
|US6287992||Apr 20, 1998||Sep 11, 2001||The Dow Chemical Company||Polymer composite and a method for its preparation|
|US6350804||Apr 14, 1999||Feb 26, 2002||General Electric Co.||Compositions with enhanced ductility|
|US6359052||Aug 1, 2000||Mar 19, 2002||Jack Wesley Trexler, Jr.||Polyester/platelet particle compositions displaying improved dispersion|
|US6376591||Dec 1, 1999||Apr 23, 2002||Amcol International Corporation||High barrier amorphous polyamide-clay intercalates, exfoliates, and nanocomposite and a process for preparing same|
|US6384121||Dec 1, 1999||May 7, 2002||Eastman Chemical Company||Polymeter/clay nanocomposite comprising a functionalized polymer or oligomer and a process for preparing same|
|US6391449||Dec 1, 1999||May 21, 2002||Amcol International Corporation||Polymer/clay intercalates, exfoliates, and nanocomposites comprising a clay mixture and a process for making same|
|US6395386||Dec 11, 1998||May 28, 2002||Eastman Chemical Company||Clear, high-barrier polymer-platelet composite multilayer structures|
|US6399690||Mar 7, 2001||Jun 4, 2002||Amcol International Corporation||Layered compositions with multi-charged onium ions as exchange cations, and their application to prepare monomer, oligomer, and polymer intercalates and nanocomposites prepared with the layered compositions of the intercalates|
|US6403231||May 12, 2000||Jun 11, 2002||Pechiney Emballage Flexible Europe||Thermoplastic film structures having improved barrier and mechanical properties|
|US6407155||Mar 1, 2000||Jun 18, 2002||Amcol International Corporation||Intercalates formed via coupling agent-reaction and onium ion-intercalation pre-treatment of layered material for polymer intercalation|
|US6417262||Dec 1, 1999||Jul 9, 2002||Eastman Chemical Company||High barrier amorphous polyamide-clay nanocomposite and a process for preparing same|
|US6447860||May 12, 2000||Sep 10, 2002||Pechiney Emballage Flexible Europe||Squeezable containers for flowable products having improved barrier and mechanical properties|
|US6461423||May 24, 2000||Oct 8, 2002||Amcol International Corporation||Intercalates and exfoliates formed with hydroxyl-functional; polyhydroxyl-functional; and aromatic compounds; composite materials containing same and methods of modifying rheology therewith|
|US6462122||Mar 1, 2000||Oct 8, 2002||Amcol International Corporation||Intercalates formed with polypropylene/maleic anhydride-modified polypropylene intercalants|
|US6469073||Dec 22, 2000||Oct 22, 2002||Ford Global Technologies, Inc.||System and method of delaminating a layered silicate material by supercritical fluid treatment|
|US6472460 *||Jun 19, 1998||Oct 29, 2002||Kabushiki Kaisha Toyota Chuo Kenkyusho||Polymer composite material and process for preparing the same|
|US6486252||Jun 22, 1999||Nov 26, 2002||Eastman Chemical Company||Nanocomposites for high barrier applications|
|US6486253||Dec 1, 1999||Nov 26, 2002||University Of South Carolina Research Foundation||Polymer/clay nanocomposite having improved gas barrier comprising a clay material with a mixture of two or more organic cations and a process for preparing same|
|US6486254||Dec 1, 1999||Nov 26, 2002||University Of South Carolina Research Foundation||Colorant composition, a polymer nanocomposite comprising the colorant composition and articles produced therefrom|
|US6534570||Aug 3, 2001||Mar 18, 2003||Southern Clay Products, Inc.||Organoclay compositions for gelling unsaturated polyester resin systems|
|US6544644 *||Jul 5, 2000||Apr 8, 2003||Rhodianyl||Abrasion resistant spun articles|
|US6548587 *||Jun 14, 2000||Apr 15, 2003||University Of South Carolina Research Foundation||Polyamide composition comprising a layered clay material modified with an alkoxylated onium compound|
|US6552113||Dec 1, 2000||Apr 22, 2003||University Of South Carolina Research Foundation||Polymer-clay nanocomposite comprising an amorphous oligomer|
|US6552114||May 13, 2002||Apr 22, 2003||University Of South Carolina Research Foundation||Process for preparing a high barrier amorphous polyamide-clay nanocomposite|
|US6586500||May 30, 2001||Jul 1, 2003||University Of South Carolina Research Foundation||Polymer nanocomposite comprising a matrix polymer and a layered clay material having an improved level of extractable material|
|US6596803||Jun 29, 2001||Jul 22, 2003||Amcol International Corporation||Layered clay intercalates and exfoliates having a low quartz content|
|US6598645||Sep 27, 2000||Jul 29, 2003||The Goodyear Tire & Rubber Company||Tire with at least one of rubber/cord laminate, sidewall insert and apex of a rubber composition which contains oriented intercalated and/or exfoliated clay reinforcement|
|US6610772||Aug 2, 2000||Aug 26, 2003||Eastman Chemical Company||Platelet particle polymer composite with oxygen scavenging organic cations|
|US6632868||Apr 25, 2001||Oct 14, 2003||Amcol International Corporation||Intercalates formed with polypropylene/maleic anhydride-modified polypropylene intercalants|
|US6635108||Nov 7, 1996||Oct 21, 2003||Southern Clay Products, Inc.||Organoclay compositions for gelling unsaturated polyester resin systems|
|US6653388||Dec 1, 1999||Nov 25, 2003||University Of South Carolina Research Foundation||Polymer/clay nanocomposite comprising a clay mixture and a process for making same|
|US6709759 *||Apr 8, 2002||Mar 23, 2004||Pechiney Emballage Flexible Europe||Thermoplastic film structures having improved barrier and mechanical properties|
|US6713547||Mar 6, 2002||Mar 30, 2004||University Of South Carolina Research Foundation||Process for preparing high barrier nanocomposites|
|US6726989 *||Feb 5, 2002||Apr 27, 2004||Fiber Innovation Technology, Inc.||Fibers including a nanocomposite material|
|US6730719||May 4, 2001||May 4, 2004||Southern Clay Products, Inc.||Process for treating smectite clays to facilitate exfoliation|
|US6737464||May 30, 2000||May 18, 2004||University Of South Carolina Research Foundation||Polymer nanocomposite comprising a matrix polymer and a layered clay material having a low quartz content|
|US6745703||Oct 26, 2001||Jun 8, 2004||Chep International, Inc.||Composite pallet member|
|US6753360||Dec 22, 2000||Jun 22, 2004||Ford Global Technologies, Llc||System and method of preparing a reinforced polymer by supercritical fluid treatment|
|US6759464||Dec 21, 2001||Jul 6, 2004||The Goodyear Tire & Rubber Company||Process for preparing nanocomposite, composition and article thereof|
|US6767951||Nov 13, 2001||Jul 27, 2004||Eastman Kodak Company||Polyester nanocomposites|
|US6767952||Nov 13, 2001||Jul 27, 2004||Eastman Kodak Company||Article utilizing block copolymer intercalated clay|
|US6777479 *||Aug 2, 2000||Aug 17, 2004||Eastman Chemical Company||Polyamide nanocomposites with oxygen scavenging capability|
|US6787592||Oct 21, 1999||Sep 7, 2004||Southern Clay Products, Inc.||Organoclay compositions prepared from ester quats and composites based on the compositions|
|US6794447||Jul 28, 2000||Sep 21, 2004||Taylor Made Golf Co., Inc.||Golf balls incorporating nanocomposite materials|
|US6828370||May 30, 2001||Dec 7, 2004||Amcol International Corporation||Intercalates and exfoliates thereof having an improved level of extractable material|
|US6833392||Nov 13, 2000||Dec 21, 2004||Lawrence A. Acquarulo, Jr.||Optimizing nano-filler performance in polymers|
|US6841211||May 12, 2000||Jan 11, 2005||Pechiney Emballage Flexible Europe||Containers having improved barrier and mechanical properties|
|US6858665||Jul 2, 2001||Feb 22, 2005||The Goodyear Tire & Rubber Company||Preparation of elastomer with exfoliated clay and article with composition thereof|
|US6861462||Dec 21, 2001||Mar 1, 2005||The Goodyear Tire & Rubber Company||Nanocomposite formed in situ within an elastomer and article having component comprised thereof|
|US6863852||May 28, 2003||Mar 8, 2005||Zeus Industrial Products, Inc.||Fluoropolymer extrusions based on novel combinations of process parameters and clay minerals|
|US6900262||Oct 1, 2001||May 31, 2005||The University Of Akron||Synthesis and characterization of nanocomposites by emulsion polymerization|
|US6911258 *||Apr 28, 2000||Jun 28, 2005||Alcatel||Optical fiber cable having improved properties|
|US6916872 *||May 30, 2003||Jul 12, 2005||Nanoproducts Corporation||Non-spherical nanopowder derived nanocomposites|
|US6988305 *||Dec 17, 1999||Jan 24, 2006||Magna International Of America, Inc.||Method and apparatus for blow molding large reinforced plastic parts|
|US7034071||Jul 20, 2004||Apr 25, 2006||Foster Corporation||Optimizing nano-filler performance in polymers|
|US7138452||Dec 11, 2002||Nov 21, 2006||Lg Chem, Ltd.||Nanocomposite blend composition having super barrier property|
|US7166656||Nov 13, 2001||Jan 23, 2007||Eastman Kodak Company||Smectite clay intercalated with polyether block polyamide copolymer|
|US7250477||Dec 11, 2003||Jul 31, 2007||General Electric Company||Thermoset composite composition, method, and article|
|US7279521||Mar 5, 2003||Oct 9, 2007||Foster Corporation||Nylon nanocomposites|
|US7309558 *||Nov 27, 2000||Dec 18, 2007||Clariant Produkte (Deutschland) Gmbh||Use of salt-like structured silicas as charge control agents|
|US7332533||Aug 25, 2004||Feb 19, 2008||Taylor Made Golf Company, Inc.||Golf balls incorporating nanofillers and methods for making such golf balls|
|US7341757||Feb 10, 2005||Mar 11, 2008||Nanoproducts Corporation||Polymer nanotechnology|
|US7368496||Mar 15, 2005||May 6, 2008||Lg Chem, Ltd.||Nanocomposite composition having super barrier property and article using the same|
|US7387673||May 20, 2003||Jun 17, 2008||Ppg Industries Ohio, Inc.||Color pigment nanotechnology|
|US7528196||Jan 18, 2006||May 5, 2009||Taylor Made Golf Company, Inc.||Polyalkenamer compositions and golf balls prepared therefrom|
|US7605205 *||Oct 20, 2009||Exxonmobil Chemical Patents, Inc.||Nanocomposite compositions and processes for making the same|
|US7625985||Dec 1, 2009||The Goodyear Tire & Rubber Company||Water-based process for the preparation of polymer-clay nanocomposites|
|US7708974||May 10, 2005||May 4, 2010||Ppg Industries Ohio, Inc.||Tungsten comprising nanomaterials and related nanotechnology|
|US7874940||Jul 13, 2006||Jan 25, 2011||Taylor Made Golf Company, Inc.||Extrusion method for making golf balls|
|US7879968||May 31, 2007||Feb 1, 2011||Taylor Made Golf Company, Inc.||Polymer compositions and golf balls with reduced yellowing|
|US7888419||Feb 15, 2011||Naturalnano, Inc.||Polymeric composite including nanoparticle filler|
|US7955382||Sep 14, 2007||Jun 7, 2011||Boston Scientific Scimed, Inc.||Endoprosthesis with adjustable surface features|
|US7985252||Jul 30, 2008||Jul 26, 2011||Boston Scientific Scimed, Inc.||Bioerodible endoprosthesis|
|US7998192||Aug 16, 2011||Boston Scientific Scimed, Inc.||Endoprostheses|
|US8002821||Aug 23, 2011||Boston Scientific Scimed, Inc.||Bioerodible metallic ENDOPROSTHESES|
|US8003726 *||Feb 14, 2008||Aug 23, 2011||Polyone Corporation||Method to establish viscosity as a function of shear rate for in-situ polymerized nanonylon via chain extension|
|US8030411||Oct 4, 2011||Taylor Made Golf Company, Inc.||Polymer compositions comprising peptizers, sports equipment comprising such compositions, and method for their manufacture|
|US8047933||Feb 13, 2009||Nov 1, 2011||Taylor Made Golf Company, Inc.||Golf ball|
|US8048150||Apr 12, 2006||Nov 1, 2011||Boston Scientific Scimed, Inc.||Endoprosthesis having a fiber meshwork disposed thereon|
|US8052743||Aug 2, 2007||Nov 8, 2011||Boston Scientific Scimed, Inc.||Endoprosthesis with three-dimensional disintegration control|
|US8052744||Sep 13, 2007||Nov 8, 2011||Boston Scientific Scimed, Inc.||Medical devices and methods of making the same|
|US8052745||Nov 8, 2011||Boston Scientific Scimed, Inc.||Endoprosthesis|
|US8057534||Sep 14, 2007||Nov 15, 2011||Boston Scientific Scimed, Inc.||Bioerodible endoprostheses and methods of making the same|
|US8058337||Nov 15, 2011||Ppg Industries Ohio, Inc.||Conductive nanocomposite films|
|US8080055||Dec 20, 2011||Boston Scientific Scimed, Inc.||Bioerodible endoprostheses and methods of making the same|
|US8089029||Feb 1, 2006||Jan 3, 2012||Boston Scientific Scimed, Inc.||Bioabsorbable metal medical device and method of manufacture|
|US8096899||Dec 17, 2008||Jan 17, 2012||Taylor Made Golf Company, Inc.||Golf ball comprising isocyanate-modified composition|
|US8113966||Oct 5, 2010||Feb 14, 2012||Taylor Made Golf Company, Inc.||Golf ball having cross-core hardness differential and method for making it|
|US8124678||Nov 27, 2007||Feb 28, 2012||Naturalnano, Inc.||Nanocomposite master batch composition and method of manufacture|
|US8128689||Sep 14, 2007||Mar 6, 2012||Boston Scientific Scimed, Inc.||Bioerodible endoprosthesis with biostable inorganic layers|
|US8211976||Jul 3, 2012||Taylor Made Golf Company, Inc.||Sports equipment compositions comprising a polyurethane, polyurea or prepolymer thereof and a polyfunctional modifier|
|US8216267||Sep 12, 2006||Jul 10, 2012||Boston Scientific Scimed, Inc.||Multilayer balloon for bifurcated stent delivery and methods of making and using the same|
|US8217108||Jul 10, 2012||Naturalnano, Inc.||Polymeric composite including nanoparticle filler|
|US8236046||Jun 10, 2008||Aug 7, 2012||Boston Scientific Scimed, Inc.||Bioerodible endoprosthesis|
|US8241150||Sep 23, 2011||Aug 14, 2012||Taylor Made Golf Company, Inc.||Golf ball|
|US8267992||Sep 18, 2012||Boston Scientific Scimed, Inc.||Self-buffering medical implants|
|US8293318||Oct 23, 2012||Abbott Cardiovascular Systems Inc.||Methods for modulating the release rate of a drug-coated stent|
|US8293812||May 19, 2005||Oct 23, 2012||The University of Queensland St. Lucia||Polymer composite|
|US8303643||Nov 6, 2012||Remon Medical Technologies Ltd.||Method and device for electrochemical formation of therapeutic species in vivo|
|US8357060||Jan 22, 2013||Taylor Made Golf Company, Inc.||Golf ball with soft feel|
|US8357756||Nov 4, 2009||Jan 22, 2013||Taylor Made Golf Company, Inc.||Compositions for sports equipment|
|US8382824||Oct 3, 2008||Feb 26, 2013||Boston Scientific Scimed, Inc.||Medical implant having NANO-crystal grains with barrier layers of metal nitrides or fluorides|
|US8389603||May 9, 2003||Mar 5, 2013||Ppg Industries Ohio, Inc.||Thermal nanocomposites|
|US8481621||Jul 6, 2012||Jul 9, 2013||Taylor Made Golf Company, Inc.||Compositions comprising an amino triazine and ionomer or ionomer precursor|
|US8501858||May 17, 2006||Aug 6, 2013||Board Of Trustees Of Michigan State University||Expanded graphite and products produced therefrom|
|US8518507||Dec 20, 2010||Aug 27, 2013||Micrus Design Technology, Inc.||Method for making a reinforced balloon with composite materials|
|US8575264 *||Jul 26, 2011||Nov 5, 2013||Polyone Corporation||Method to establish viscosity as a function of shear rate for in-situ polymerized nanonylon via chain extension|
|US8575278||Dec 21, 2010||Nov 5, 2013||Taylor Made Golf Company, Inc.||Ionomer compositions for golf balls|
|US8608993||Mar 22, 2011||Dec 17, 2013||The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration||Mechanically strong, thermally stable, and electrically conductive nanocomposite structure and method of fabricating same|
|US8629228||Dec 21, 2010||Jan 14, 2014||Taylor Made Golf Company, Inc.||Ionomer compositions for golf balls|
|US8632423||Jul 18, 2012||Jan 21, 2014||Taylor Made Golf Company, Inc.||Golf ball|
|US8637111||Sep 6, 2012||Jan 28, 2014||Abbott Cardiovascular Systems Inc.||Methods for modulating the release rate of a drug-coated stent|
|US8648132||Feb 7, 2008||Feb 11, 2014||Naturalnano, Inc.||Nanocomposite method of manufacture|
|US8668732||Mar 22, 2011||Mar 11, 2014||Boston Scientific Scimed, Inc.||Surface treated bioerodible metal endoprostheses|
|US8674010 *||Dec 22, 2005||Mar 18, 2014||Polyone Corporation||Blends of nanocomposites and their use|
|US8674023||Dec 21, 2010||Mar 18, 2014||Taylor Made Golf Company, Inc.||Ionomer compositions for golf balls|
|US8715113||Sep 14, 2012||May 6, 2014||Eric M. Loper||Golf ball with soft feel|
|US8715339||Nov 21, 2011||May 6, 2014||Boston Scientific Scimed, Inc.||Bioerodible endoprostheses and methods of making the same|
|US8728170||Mar 30, 2007||May 20, 2014||Boston Scientific Scimed, Inc.||Bioerodible nano-fibrous and nano-porous conductive composites|
|US8758429||Sep 6, 2012||Jun 24, 2014||Micell Technologies, Inc.||Polymer coatings containing drug powder of controlled morphology|
|US8764586||Nov 8, 2011||Jul 1, 2014||Taylor Made Golf Company, Inc.||Golf ball having cross-core hardness differential and method for making it|
|US8772409||Sep 14, 2012||Jul 8, 2014||Taylor Made Golf Company, Inc.||Compositions for sports equipment|
|US8785561||Mar 31, 2009||Jul 22, 2014||Taylor Made Golf Company, Inc.||Polyalkenamer compositions and golf balls prepared therefrom|
|US8795762||Mar 26, 2010||Aug 5, 2014||Battelle Memorial Institute||System and method for enhanced electrostatic deposition and surface coatings|
|US8808726||Sep 14, 2007||Aug 19, 2014||Boston Scientific Scimed. Inc.||Bioerodible endoprostheses and methods of making the same|
|US8809428||Dec 22, 2009||Aug 19, 2014||Taylor Made Golf Company, Inc.||Golf ball|
|US8815362||Aug 5, 2013||Aug 26, 2014||DePuy Synthes Products, LLC||Method for making a reinforced balloon with composite materials|
|US8834913||Dec 28, 2009||Sep 16, 2014||Battelle Memorial Institute||Medical implants and methods of making medical implants|
|US8840660||Jan 5, 2006||Sep 23, 2014||Boston Scientific Scimed, Inc.||Bioerodible endoprostheses and methods of making the same|
|US8852625||Apr 26, 2007||Oct 7, 2014||Micell Technologies, Inc.||Coatings containing multiple drugs|
|US8900651 *||Dec 4, 2008||Dec 2, 2014||Micell Technologies, Inc.||Polymer films for medical device coating|
|US8912286||Oct 3, 2011||Dec 16, 2014||Taylor Made Golf Company, Inc.||Polymer compositions comprising peptizers, sports equipment comprising such compositions, and method for their manufacture|
|US8926776||Jan 2, 2008||Jan 6, 2015||DePuy Synthes Products, LLC||Method for making a reinforced balloon with composite materials|
|US8932154||Dec 23, 2008||Jan 13, 2015||Taylor Made Golf Company, Inc.||Golf ball with softer feel and high iron spin|
|US8979677||Nov 24, 2010||Mar 17, 2015||Taylor Made Golf Company, Inc.||Golf ball with selected spin characteristics|
|US8992341||Dec 23, 2009||Mar 31, 2015||Taylor Made Golf Company, Inc.||Injection moldable compositions and golf balls prepared therefrom|
|US9108082||Dec 19, 2011||Aug 18, 2015||Taylor Made Golf Company, Inc.||Golf ball composition|
|US20020037953 *||May 30, 2001||Mar 28, 2002||Tie Lan||Intercalates and exfoliates thereof having an improved level of extractable material|
|US20030100655 *||Nov 13, 2001||May 29, 2003||Eastman Kodak Company||Polyester nanocomposites|
|US20030100656 *||Nov 13, 2001||May 29, 2003||Eastman Kodak Company||Smectite clay intercalated with polyether block polyamide copolymer|
|US20030149154 *||Jun 14, 2001||Aug 7, 2003||Klaus Heinemann||Method for producing nanoreinforced thermoplastic polymers|
|US20030153670 *||Apr 30, 2001||Aug 14, 2003||Dirk Pophusen||Reinforced polyamide with improved thermal ageing properties|
|US20030207976 *||May 9, 2003||Nov 6, 2003||Tapesh Yadav||Thermal nanocomposites|
|US20030207978 *||May 30, 2003||Nov 6, 2003||Tapesh Yadav||Non-spherical nanopowder derived nanocomposites|
|US20030209057 *||May 20, 2003||Nov 13, 2003||Tapesh Yadav||Color pigment nanotechnology|
|US20040030022 *||Oct 1, 2001||Feb 12, 2004||Brittain William J.||Synthesis and characterization of nanocomposites by emulsion polymerization|
|US20040054059 *||Dec 21, 2001||Mar 18, 2004||Parker Dane Kenton||Preparation and use of a nanocomposite of elastomer and exfoliated clay platelets formed in situ within an elastomer host and articles of manufacture, including tires, having at least one component comprised thereof|
|US20040063841 *||Sep 30, 2003||Apr 1, 2004||Gilmer John Walker||Process for preparing an exfoliated, high I. V. polymer nanocomposite with an oligomer resin precursor and an article produced therefrom|
|US20040082698 *||Oct 14, 2003||Apr 29, 2004||Barbee Robert Boyd||Polymer/clay nanocomposite comprising a clay mixture and a process for making same|
|US20040092336 *||Sep 24, 2003||May 13, 2004||Kim Hyun Jim||Golf balls incorporating nanocomposite and/or nanofiller materials|
|US20040101559 *||Nov 25, 2002||May 27, 2004||David Wong||Novel pharmaceutical formulations|
|US20040106719 *||Dec 11, 2002||Jun 3, 2004||Myung-Ho Kim||Nanocomposite blend composition having super barrier property|
|US20040110884 *||Nov 13, 2001||Jun 10, 2004||Eastman Kodak Company||Article utilizing block copolymer intercalated clay|
|US20040122153 *||Dec 11, 2003||Jun 24, 2004||Hua Guo||Thermoset composite composition, method, and article|
|US20040127627 *||Jul 30, 2003||Jul 1, 2004||Gilmer John Walker||Polymer/clay nanocomposite comprising a clay treated with a mixture of two or more onium salts and a process for making same|
|US20040139888 *||Oct 6, 2003||Jul 22, 2004||Tapesh Yadav||Printing inks and reagents for nanoelectronics and consumer products|
|US20040178530 *||Oct 31, 2003||Sep 16, 2004||Tapesh Yadav||High volume manufacturing of nanoparticles and nano-dispersed particles at low cost|
|US20040241482 *||Jun 2, 2003||Dec 2, 2004||Grah Michael D.||PVdC film with nanocomposite tie layer|
|US20040259969 *||Jul 20, 2004||Dec 23, 2004||Acquarulo Lawrence A.||Optimizing nano-filler performance in polymers|
|US20050059756 *||Aug 25, 2004||Mar 17, 2005||Taylor Made Golf Company, Inc.||Golf balls incorporating nanofillers|
|US20050065263 *||Sep 22, 2003||Mar 24, 2005||Chung James Y.J.||Polycarbonate composition|
|US20050119371 *||Oct 15, 2004||Jun 2, 2005||Board Of Trustees Of Michigan State University||Bio-based epoxy, their nanocomposites and methods for making those|
|US20050147747 *||Feb 10, 2005||Jul 7, 2005||Tapesh Yadav||Polymer nanotechnology|
|US20050159526 *||Jan 15, 2004||Jul 21, 2005||Bernard Linda G.||Polymamide nanocomposites with oxygen scavenging capability|
|US20050215694 *||Mar 15, 2005||Sep 29, 2005||Myung-Ho Kim||Nanocomposite composition having super barrier property and article using the same|
|US20050271566 *||May 10, 2005||Dec 8, 2005||Nanoproducts Corporation||Tungsten comprising nanomaterials and related nanotechnology|
|US20060111499 *||Oct 20, 2005||May 25, 2006||Kim Myung H||Nanocomposite composition having high barrier property|
|US20060128505 *||Feb 9, 2006||Jun 15, 2006||Sullivan Michael J||Golf ball layers having improved barrier properties|
|US20060161130 *||Jan 14, 2005||Jul 20, 2006||Kimberly-Clark Worldwide, Inc.||Disposable absorbent article visually appearing similar to cloth underwear|
|US20060166762 *||Jan 18, 2006||Jul 27, 2006||Taylor Made Golf Company, Inc.||Polyalkenamer compositions and golf balls prepared therefrom|
|US20060173116 *||Jan 20, 2006||Aug 3, 2006||Trw Automotive Safety Systems Gmbh||Gas bag module|
|US20060231792 *||May 17, 2006||Oct 19, 2006||Board Of Trustees Of Michigan State University||Expanded graphite and products produced therefrom|
|US20060235136 *||Apr 12, 2006||Oct 19, 2006||Administrator Of The National Aeronautics And Space Administration||Mechanically strong, thermally stable, and electrically conductive nanocomposite structure and method of fabricating same|
|US20060264523 *||Feb 18, 2004||Nov 23, 2006||Min-Hee Lee||Polyvinyl chloride foams|
|US20070009564 *||Jun 22, 2005||Jan 11, 2007||Mcclain James B||Drug/polymer composite materials and methods of making the same|
|US20070015605 *||Jul 13, 2006||Jan 18, 2007||Taylor Made Golf Company, Inc.||Extrusion method for making golf balls|
|US20070078212 *||Sep 21, 2006||Apr 5, 2007||Lg Chem, Ltd.||Nanocomposite composition having barrier property and product using the same|
|US20070100085 *||Nov 1, 2006||May 3, 2007||Taylor Made Golf Company, Inc.||Amide-modified polymer compositions and sports equipment made using the compositions|
|US20070105998 *||Nov 7, 2005||May 10, 2007||Caiguo Gong||Nanocomposite compositions and processes for making the same|
|US20070106006 *||Aug 31, 2006||May 10, 2007||Naturalnano, Inc.||Polymeric composite including nanoparticle filler|
|US20070142568 *||Dec 15, 2006||Jun 21, 2007||Taylor Made Golf Company, Inc.||Polymer compositions comprising peptizers, sports equipment comprising such compositions, and method for their manufacture|
|US20070148457 *||Sep 13, 2006||Jun 28, 2007||Naturalnano, Inc.||Radiation absorptive composites and methods for production|
|US20070156231 *||Jan 5, 2006||Jul 5, 2007||Jan Weber||Bioerodible endoprostheses and methods of making the same|
|US20070161737 *||Jan 9, 2006||Jul 12, 2007||Bayer Materialscience Llc||Thermoplastic composition containing polycarbonate-polyester and nanoclay|
|US20070161738 *||Jan 31, 2007||Jul 12, 2007||Bayer Materialscience Llc||Thermoplastic composition containing polycarbonate-polyester and nanoclay|
|US20070178129 *||Feb 1, 2006||Aug 2, 2007||Boston Scientific Scimed, Inc.||Bioabsorbable metal medical device and method of manufacture|
|US20070178299 *||Jul 21, 2006||Aug 2, 2007||Verrall Andrew P||Water-soluble composition and structures, and methods of making and using the same|
|US20070224244 *||Mar 22, 2006||Sep 27, 2007||Jan Weber||Corrosion resistant coatings for biodegradable metallic implants|
|US20070244569 *||Apr 12, 2006||Oct 18, 2007||Jan Weber||Endoprosthesis having a fiber meshwork disposed thereon|
|US20080065188 *||Sep 12, 2006||Mar 13, 2008||Boston Scientific Scimed, Inc.||Multilayer balloon for bifurcated stent delivery and methods of making and using the same|
|US20080071350 *||Sep 13, 2007||Mar 20, 2008||Boston Scientific Scimed, Inc.||Endoprostheses|
|US20080071351 *||Sep 14, 2007||Mar 20, 2008||Boston Scientific Scimed, Inc.||Endoprosthesis with adjustable surface features|
|US20080071352 *||Sep 14, 2007||Mar 20, 2008||Boston Scientific Scimed, Inc.||Bioerodible endoprosthesis with biostable inorganic layers|
|US20080071358 *||Sep 13, 2007||Mar 20, 2008||Boston Scientific Scimed, Inc.||Endoprostheses|
|US20080082162 *||Sep 14, 2007||Apr 3, 2008||Boston Scientific Scimed, Inc.||Bioerodible endoprostheses and methods of making the same|
|US20080086201 *||Sep 14, 2007||Apr 10, 2008||Boston Scientific Scimed, Inc.||Magnetized bioerodible endoprosthesis|
|US20080095919 *||Oct 23, 2007||Apr 24, 2008||Mcclain James B||Holder For Electrically Charging A Substrate During Coating|
|US20080097577 *||Sep 18, 2007||Apr 24, 2008||Boston Scientific Scimed, Inc.||Medical device hydrogen surface treatment by electrochemical reduction|
|US20080109072 *||Sep 13, 2007||May 8, 2008||Boston Scientific Scimed, Inc.||Medical devices and methods of making the same|
|US20080131479 *||Aug 2, 2007||Jun 5, 2008||Jan Weber||Endoprosthesis with three-dimensional disintegration control|
|US20080142764 *||Jun 12, 2007||Jun 19, 2008||Nanoproducts Corporation||Conductive nanocomposite films|
|US20080161906 *||Dec 27, 2007||Jul 3, 2008||Boston Scientific Scimed, Inc.||Bioerodible endoprostheses and methods of making the same|
|US20080176677 *||Dec 27, 2007||Jul 24, 2008||Taylor Made Golf Company, Inc.||Golf balls with improved feel|
|US20080188587 *||Dec 22, 2005||Aug 7, 2008||Polyone Corporation||Blends of Nanocomposites and their Use|
|US20080214326 *||Jan 23, 2008||Sep 4, 2008||Taylor Made Golf Company, Inc.||Golf balls incorporating nanofillers|
|US20080248201 *||Apr 6, 2007||Oct 9, 2008||Naturalnano Research, Inc.||Polymeric coatings including nanoparticle filler|
|US20080249221 *||Apr 6, 2007||Oct 9, 2008||Naturalnano Research, Inc.||Polymeric adhesive including nanoparticle filler|
|US20080262126 *||Feb 7, 2008||Oct 23, 2008||Naturalnano, Inc.||Nanocomposite method of manufacture|
|US20080281016 *||May 19, 2005||Nov 13, 2008||Darren James Martin||Polymer Composite|
|US20080302733 *||May 7, 2008||Dec 11, 2008||Amcol International Corporation||Coupling agent-reacted mercury removal media|
|US20090061212 *||Aug 12, 2008||Mar 5, 2009||Wurtzel Kenneth C||Reduced Crystallizing Aromatic Nylon|
|US20090076588 *||Sep 13, 2007||Mar 19, 2009||Jan Weber||Endoprosthesis|
|US20090143855 *||Nov 29, 2007||Jun 4, 2009||Boston Scientific Scimed, Inc.||Medical Device Including Drug-Loaded Fibers|
|US20090170633 *||Dec 17, 2008||Jul 2, 2009||Taylor Made Golf Company, Inc.||Isocyanate-modified composition|
|US20090170634 *||Dec 23, 2008||Jul 2, 2009||Taylor Made Golf Company||Golf ball with soft feel|
|US20090175985 *||Jul 27, 2006||Jul 9, 2009||Leigh Trevor Canham||Food Comprising Silicon|
|US20090176601 *||Dec 23, 2008||Jul 9, 2009||Taylor Made Golf Company||Golf ball with softer feel and high iron spin|
|US20090186069 *||Apr 26, 2007||Jul 23, 2009||Micell Technologies, Inc.||Coatings Containing Multiple Drugs|
|US20090191981 *||Mar 31, 2009||Jul 30, 2009||Taylor Made Golf Company, Inc.||Polyalkenamer compositions and golf balls prepared therefrom|
|US20090209367 *||Feb 13, 2009||Aug 20, 2009||Taylor Made Golf Company, Inc.||Golf ball|
|US20090281613 *||May 9, 2008||Nov 12, 2009||Boston Scientific Scimed, Inc.||Endoprostheses|
|US20090292351 *||Nov 26, 2009||Micell Technologies, Inc.||Stents having bioabsorbable layers|
|US20090326133 *||May 23, 2008||Dec 31, 2009||Naturalnano Research, Inc.||Fire and flame retardant polymer composites|
|US20100008970 *||Jan 14, 2010||Boston Scientific Scimed, Inc.||Drug-Eluting Endoprosthesis|
|US20100015200 *||Jul 16, 2009||Jan 21, 2010||Micell Technologies, Inc.||Drug Delivery Medical Device|
|US20100029816 *||Feb 14, 2008||Feb 4, 2010||Polyone Corporation||Method to establish viscosity as a function of shear rate for in-situ polymerized nanonylon via chain extension|
|US20100030326 *||Jul 30, 2008||Feb 4, 2010||Boston Scientific Scimed, Inc.||Bioerodible Endoprosthesis|
|US20100063580 *||Jan 8, 2008||Mar 11, 2010||Mcclain James B||Stents having biodegradable layers|
|US20100087910 *||Apr 8, 2010||Jan Weber||Medical implant|
|US20100125002 *||Sep 25, 2009||May 20, 2010||Taylor Made Golf Company, Inc.||Resin compositions incorporating modified polyisocyanate and method for their manufacture and use|
|US20100160079 *||Nov 4, 2009||Jun 24, 2010||Taylor Made Golf Company, Inc.||Compositions for sports equipment|
|US20100211164 *||Apr 17, 2008||Aug 19, 2010||Mcclain James B||Stents having biodegradable layers|
|US20100222873 *||Sep 2, 2010||Boston Scientific Scimed, Inc.||Self-Buffering Medical Implants|
|US20100228348 *||May 23, 2008||Sep 9, 2010||Micell Technologies, Inc.||Polymer Films for Medical Device Coating|
|US20100241220 *||Sep 23, 2010||Mcclain James B||Peripheral Stents Having Layers|
|US20100256748 *||Mar 31, 2010||Oct 7, 2010||Micell Technologies, Inc.||Coated stents|
|US20100272778 *||Apr 16, 2010||Oct 28, 2010||Micell Technologies, Inc.||Stents having controlled elution|
|US20100298928 *||Oct 17, 2008||Nov 25, 2010||Micell Technologies, Inc.||Drug Coated Stents|
|US20100323818 *||Aug 31, 2010||Dec 23, 2010||Taylor Made Golf Company, Inc.||Extrusion method for making golf balls|
|US20110022158 *||Jul 22, 2009||Jan 27, 2011||Boston Scientific Scimed, Inc.||Bioerodible Medical Implants|
|US20110086956 *||Nov 27, 2007||Apr 14, 2011||Naturalnano, Inc.||Nanocomposite master batch composition and method of manufacture|
|US20110124439 *||May 26, 2011||Taylor Made Golf Company, Inc.||Polymer compositions and golf balls with reduced yellowing|
|US20110130216 *||Jun 2, 2011||Taylor Made Golf Company, Inc.||Golf ball constructs and related systems|
|US20110147237 *||Jul 29, 2009||Jun 23, 2011||Colgate-Palmolive Company||Uv-protected container with products having dyes or lakes|
|US20110152008 *||Jun 23, 2011||Kim Hyun J||Injection moldable compositions and golf balls prepared therefrom|
|US20110159069 *||Dec 28, 2009||Jun 30, 2011||Shaw Wendy J||Medical Implants and Methods of Making Medical Implants|
|US20110159991 *||Dec 29, 2010||Jun 30, 2011||Taylor Made Golf Company, Inc.||Golf ball composition|
|US20110159992 *||Jun 30, 2011||Taylor Made Golf Company, Inc.||Ionomer compositions for golf balls|
|US20110159994 *||Jun 30, 2011||Taylor Made Golf Company, Inc.||Ionomer compositions for golf balls|
|US20110160345 *||Jan 10, 2011||Jun 30, 2011||Naturalnano, Inc.||Polymeric composite including nanoparticle filler|
|US20110190864 *||Aug 4, 2011||Micell Technologies, Inc.||Stent and stent delivery system with improved deliverability|
|US20110238151 *||Sep 29, 2011||Boston Scientific Scimed, Inc.||Surface treated bioerodible metal endoprostheses|
|US20110238161 *||Sep 29, 2011||Battelle Memorial Institute||System and method for enhanced electrostatic deposition and surface coatings|
|US20110281996 *||Nov 17, 2011||Polyone Corporation|
|US20150368410 *||Dec 18, 2013||Dec 24, 2015||Agency For Science, Technology And Research||Method of preparing fiber-reinforced polymer composites and fiber-reinforced polymer composites prepared thereof|
|DE10115541A1 *||Mar 28, 2001||Oct 10, 2002||Henkel Kgaa||Derivatisierte Schichtsilikate und ihre Verwendung in der Haarpflege|
|EP1054922A1 *||Feb 13, 1998||Nov 29, 2000||Solutia Inc.||Polymer nanocomposite composition|
|EP1717264A1 *||Apr 29, 2005||Nov 2, 2006||Campine||Process for producing a polyamide and/or polyester composition comprising nanoclay|
|EP2258753A1||May 10, 2001||Dec 8, 2010||Pechiney Emballage Flexible Europe||Thermoplastic film structures having improved barrier and mechanical properties|
|WO1997031973A1 *||Feb 27, 1997||Sep 4, 1997||E.I. Du Pont De Nemours And Company||Composite material and production of the composite material, and composite-material-containing resin composition and production of the resin composition|
|WO2000034372A1 *||Dec 7, 1999||Jun 15, 2000||Eastman Chemical Company||A high barrier amorphous polyamide-clay nanocomposite and a process for preparing same|
|WO2000058071A1 *||Feb 25, 2000||Oct 5, 2000||Anderlik, Rainer||Method of incorporating at least one solids powder a into a melt containing at least a thermoplastic polymer b|
|WO2001087566A1 *||May 10, 2001||Nov 22, 2001||Pechiney Emballage Flexible Europe||Thermoplastic film structures having improved barrier and mechanical properties|
|WO2001087580A1 *||May 10, 2001||Nov 22, 2001||Pechiney Emballage Flexible Europe||Containers having improved barrier and mechanical properties|
|WO2002094534A1 *||May 17, 2002||Nov 28, 2002||Basf Aktiengesellschaft||Method for the production of castings from polyamide nanocomposites|
|WO2004110739A1 *||Apr 27, 2004||Dec 23, 2004||Rehau Ag + Co||Polymeric diffusion and wear-protection layers for plastic drinking water supply lines|
|WO2006024068A1 *||May 19, 2005||Mar 9, 2006||The University Of Queensland||Polymer composite|
|WO2007035031A1 *||Sep 11, 2006||Mar 29, 2007||Lg Chem, Ltd.||Nanocomposite composition having barrier property and product using the same|
|WO2009032596A1 *||Aug 25, 2008||Mar 12, 2009||Alcan Global Pharmaceutical Packaging Inc.||Reduced crystallizing aromatic nylon|
|WO2014021800A2||Jul 9, 2013||Feb 6, 2014||Rich Group Kimyevi Maddeler Insaat Sanayi Ve Ticaret Limited Sirketi||Green technology line for production of clay micro- and nanoparticles and their functional polymer nanohybrids for nanoengineering and nanomedicine applications|
|U.S. Classification||428/297.4, 524/789, 428/477.7, 428/372, 428/331, 428/374, 428/475.5|
|International Classification||C08K7/00, C08K7/02, C08K3/34, C08L77/00, C08K7/04|
|Cooperative Classification||Y10T428/31765, Y10T428/31739, Y10T428/24994, Y10T428/259, C08K7/00, Y10T428/2927, C08K7/04, Y10T428/2931|
|European Classification||C08K7/00, C08K7/04|
|Nov 16, 1992||AS||Assignment|
Owner name: ALLIED-SIGNAL INC., NEW JERSEY
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:MAXFIELD, MACRAE;CHRISTIANI, BRIAN R.;MURTHY, SANJEEVA N.;AND OTHERS;REEL/FRAME:006380/0339
Effective date: 19921112
Owner name: ALLIED-SIGNAL INC., NEW JERSEY
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:TULLER, HAROLD;REEL/FRAME:006380/0342
Effective date: 19921112
|Sep 23, 1993||AS||Assignment|
Owner name: ALLIEDSIGNAL INC., NEW JERSEY
Free format text: CHANGE OF NAME;ASSIGNOR:ALLIED-SIGNAL INC.;REEL/FRAME:006704/0091
Effective date: 19930426
|Jun 30, 1998||FPAY||Fee payment|
Year of fee payment: 4
|Jul 1, 2002||FPAY||Fee payment|
Year of fee payment: 8
|Jun 22, 2006||FPAY||Fee payment|
Year of fee payment: 12